Polyglyceryl compounds and compositions

ABSTRACT

Provided are compositions comprising one or more compounds having a structure comprising a node structure with from four to twelve carbon atoms, one or more (poly)glyceryl groups, and one or more hydrophobic moieties, wherein each of the one or more (poly)glyceryl groups is linked to the node structure by a first primary linking group, the one or more hydrophobic moieties are each independently linked either to the node structure by a primary linking group or to one of the (poly)glyceryl groups by a secondary linking group, and wherein the polyglyceryl thickener has an average degree of glyceryl polymerization of from greater than 3 to less than about 11 and an average number of hydrophobic groups per primary linking group of about 0.35 or greater. Also provided are polyglyceryl compounds, compositions comprising water, a surfactant, and a polyglyceryl thickener, as well as, methods of making polyglyceryl compounds and compositions of the present invention.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of priority of the provisionalapplication, Application Ser. No. 61/413712, filed Nov. 15, 2010 andincorporated herein in its entirety by reference.

FIELD OF INVENTION

The present invention relates to polyglyceryl thickeners andcompositions comprising polyglyceryl thickeners that are useful in avariety of applications including cleansing of the human body.

DESCRIPTION OF THE RELATED ART

Synthetic detergents, such as cationic, anionic, amphoteric, andnon-ionic surfactants, are used widely in a variety of detergent andcleansing compositions to impart cleansing properties thereto. Inaddition, in certain compositions (e.g. personal care compositions suchas shampoos, washes, etc.), it may be desirable to combine surfactantsand ingredients such as thickeners to achieve relatively a desirablebalance of properties such as mildness, foam volume, foam stability, andrheological behavior.

A commonly used class of thickeners are amphiphilic molecules that havelarge hydrophilic head groups and are highly ethoxylated, oftencomprising greater than 100 moles of ethylene oxide (EO). Unfortunately,ethoxylation requires tremendous volumes of EO, a gaseous petrochemicalderivative synthesized via air-oxidation of ethylene gas. In addition tobeing a difficult-to-handle chemical with significant health and safetyrisks, EO is considered by many to be unsustainable in the long term dueto finite reserves of crude oil and natural gas in the world.Furthermore, a byproduct of ethoxylation processes is the cyclic ether1,4-dioxane, a suspected carcinogen at high exposure levels. Ethoxylatedmaterials typically contain trace levels (10-100 ppm) of 1,4-dioxane,and special separation processes (e.g. vacuum stripping) must beemployed to reduce the level of 1,4-dioxane to undetectable levels. Whenpresent in cleansing compositions at trace levels, 1,4-dioxane is notconsidered to be a credible health or safety risk. Nevertheless,negative publicity associated with 1,4-dioxane has provided motivationto seek products that do not have ethoxylated materials.

The inventors have recognized that it would be desirable to replacesynthetic ethoxylated thickeners with more natural and renewablematerials. However, natural thickeners such as vegetable gums typicallyhave a stringy, pseudoplastic, and/or elastic rheology that is lessaesthetically desirable. Accordingly, the inventors have recognized thatit is highly desirable to formulate compositions that have morenaturally-derived and/or renewable thickeners to alleviate theaforementioned drawbacks. The inventors have further recognized thatthickeners that do not require ethoxylation are highly desirable,particularly thickeners that are capable of thickening a range ofpersonal care product formulations in manner that is aestheticallyacceptable to consumers.

SUMMARY OF THE INVENTION

The present invention provides polyglyceryl thickeners that overcome thedisadvantages of the prior art and are capable of enhancing theviscosity of compositions to which they are added.

According to one aspect, the present invention provides polyglycerylcompositions comprising one or more compounds, having a structurecomprising a node structure with from four to twelve carbon atoms, oneor more (poly)glyceryl groups, and one or more hydrophobic moieties,wherein each of the one or more (poly)glyceryl groups is linked to thenode structure by a first primary linking group, the one or morehydrophobic moieties are each independently linked either to the nodestructure by a primary linking group or to one of the (poly)glycerylgroups by a secondary linking group, and wherein the polyglycerylthickener has an average degree of glyceryl polymerization of fromgreater than 3 to about 11 and an average number of hydrophobic groupsper primary linking group of about 0.35 or greater.

According to another aspect, the present invention provides polyglycerylcompounds, and/or compositions comprising one or more compounds, of theFormula I:

wherein:

Z is a node structure comprising from four to twelve carbon atoms;

each G is an independently selected (poly)glyceryl group;

each (Hphob) is an independently selected hydrophobic moiety;

each L is an independently selected primary linking group;

each L′ is an independently selected primary linking group;

each L″ is an independently selected secondary linking group;

each (Nu) is an independently selected nucleophilic group;

x is from 1 to 12;

h is from 0 to 11;

y is from 0 to 5;

a is from 0 to 11;

the sum of x+h+a is from 4 to 12; and

the sum of h+y is from 1 to 12.

According to another aspect, the present invention provides compositionscomprising a base comprising water and a surfactant, and a polyglycerylthickener having a structure comprising a node structure with from fourto twelve carbon atoms, one or more (poly)glyceryl groups, and one ormore hydrophobic moieties, wherein each of the one or more(poly)glyceryl groups is linked to the node structure by a first primarylinking group, the one or more hydrophobic moieties are eachindependently linked either to the node structure by a primary linkinggroup or to one of the (poly)glyceryl groups by a secondary linkinggroup, and wherein the polyglyceryl thickener has an average degree ofglyceryl polymerization of greater than 3 and an average number ofhydrophobic groups per primary linking group of about 0.35 or greater,and wherein said polyglyceryl thickener is present in a concentrationsufficient to increase the Zero Shear Viscosity of the base by about 100cP or more.

According to other aspects, the present invention provides methods ofmaking polyglyceryl thickeners, and methods of cleansing the human bodyby contacting the body with a composition of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graphical depiction of the relative viscosity compared tobase as function of DP_(g) measured for certain compositions of theclaimed invention.

FIG. 2 is a graphical depiction of the relative viscosity compared tobase as a function of wt % of polyglyceryl thickener in a formulationmeasured for certain compositions of the claimed invention.

FIG. 3 is an ¹H NMR spectrum for a composition E1A as made in accordwith the Examples.

FIG. 4 is an illustration of 40 reference protons (indicated by a *)used as an internal reference to determine DP_(g) for a composition E1Aas made in accord with the Examples.

DESCRIPTION OF PREFERRED EMBODIMENTS

All percentages listed in this specification are percentages by weight,unless otherwise specifically mentioned.

As used herein, the term “healthcare” refers to the fields of personalcare and medical care including, but not limited to, infant care, oralcare, sanitary protection, skin care, including the treatment of adultor infant skin to maintain the health of the skin, improve the health ofthe skin, and/or improve the appearance of the skin, wound care,including the treatment of a wound to assist in the closure or healingof a wound, and/or to reduce the pain or scarring associated with thewound, women's health, including the treatment of tissue in the internalor external vaginal area and/or breast, maintaining or improving thehealth of such tissue or skin, repairing such tissue or skin, reducingirritation of such tissue or skin, maintaining or improving theappearance of such tissue or skin, and improving or enhancing sexualfunction associated with such tissue or skin, and the like.

As noted above, applicants have discovered unexpectedly that certainpolyglyceryl compounds or compositions can be used to thicken cosmeticand personal care bases. In particular, applicants have noted theunexpected properties associated with the use of certain embodiments ofpolyglyceryl compositions that have both an average degree of glycerylpolymerization greater than three and at least about 0.35 averagehydrophobic moieties per primary linking group. The resultingcompositions may be suitable for use as cleansing and/or rinse-offcompositions.

In certain embodiments, polyglyceryl compounds and compositions of thepresent invention may be described with reference to the followingstructure (Formula I):

where, according to this embodiment:

-   Z is a node structure;-   each G is an independently selected (poly)glyceryl group;-   each L is an independently selected primary linking group (linking a    (poly)glyceryl group to the node structure);-   x is the number of (poly)glyceryl groups per polyglyceryl molecule,    which is from 1 to 12;-   each (Hphob) is an independently selected hydrophobic moiety;-   each L′ is an independently selected primary linking group (linking    a hydrophobic moiety to the node structure);-   h is the number of hydrophobic moieties that are linked to the node    structure via a linking group L′, which is from 0 to 11;-   each L″ is an independently selected secondary linking group    (linking a hydrophobic moiety to a glyceryl group);-   y is the number of hydrophobic moieties that are linked to a    (poly)glyceryl group via a secondary linking group L″, which is from    0 to 5;-   each (Nu) is an independently selected nucleophilic group;-   a is the number of nucleophilic groups, which is from 0 to 11;-   the sum of x+h+a is from 4 to 12; and-   the sum of h+y is from 1 to 12.

Accordingly, polyglyceryl materials of the present invention comprisecompounds having a node structure (Z) to which (poly)glyceryl units arelinked via a primary linking group (L). Suitable node structures includelinear, branched, or cyclic, saturated or unsaturated polynucleophileremnants comprising from four to twelve carbon atoms, and optionally,one or more heteroatoms such as oxygen, nitrogen, or sulfur. As usedherein the term “polynucleophile” means a compound having a plurality ofnucleophilic functional groups or groups capable of being renderednucleophilic, for example, hydroxyl (—OH), thio (—SH), amino (—NR, whereR is H or CH₃), carboxy (—COO⁻) groups, and the like. Examples ofpolynucleophiles include: polyols such as monosaccharides, e.g. glucose,fructose, galactose, mannose, glucosamine; C₁-C₄ glucosides,disaccharides (e.g. sucrose), sugar alcohols (e.g. sorbitol, xylitol,mannitol), anhydro sugar alcohols (e.g. sorbitan), pentaerythritol,oligoglycerols (e.g. diglycerol, triglycerol),N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine,N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine, and the like.

The term “polynucleophile remnant” as used herein refers to thestructure of a polynucleophile compound with all of the terminalnucleophilic groups (e.g. hydroxyl groups) removed. For example, apolynucleophilic remnant derived from methyl glucoside would be thestructure of methyl glucoside with the four hydroxyl groups removedtherefrom as shown below:

which results in a node structure which is a 5-carbon cyclic etherhaving a methylene at the 5-position and a methyl ether at the1-position. Other examples include polynucleophilic remnants derivedfrom sorbitan (wherein removal of the four hydroxyl groups results in anode structure that is a 4-carbon cyclic ether with an ethyl group atthe 2-position):

and triglycerol (wherein removal of the five hydroxyl groups results ina 1,3,-dipropoxypropane node structure):

and the like. According to certain preferred embodiments, the nodestructure has from about 6 to about 9 carbons, in certain more preferredembodiments from about 6 to about 7 carbons. According to certainpreferred embodiments, the node structure is a polynucleophile remnantderived from a polynucleophile selected from the group consisting ofpolyols such as monosaccharides, e.g. glucose, fructose, galactose,mannose, glucosamine; C₁-C₄ glucosides, disaccharides (e.g. sucrose),sugar alcohols (e.g. sorbitol, xylitol, mannitol), anhydro sugaralcohols (e.g. sorbitan), pentaerythritol, oligoglycerols (e.g.diglycerol, triglycerol),N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine, andN,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine. In certain morepreferred embodiments, the node structure is a polynucleophile remnantderived from methyl glucoside, sorbitan, diglycerol, or triglycerol, orin other more preferred embodiments, from methyl glucoside, diglycerol,or triglycerol.

The polyglyceryl materials of the present invention comprise one or more(poly)glyceryl groups (G). As used herein a “(poly)glyceryl group” meansa group linked to the node through a primary linking group (L)comprising one glyceryl unit, a plurality of glyceryl units linkedtogether in sequence, and/or one or more glyceryl units linked withco-repeat units as part of a glyceryl copolymer group. The term“glyceryl unit” means a linear, branched, and/or cyclic ether-comprisingmoiety that is a structural derivative of glycerol (C₃H₈O₃), such asunits corresponding to dehydrated glycerol (C₃H₆O₂). Those skilled inthe art will recognize, the glyceryl units may be present as singleunits in a particular glyceryl group or may repeat such that a pluralityof such units are present in a given (poly)glyceryl group.

Examples of certain glyceryl units are represented as linear-1,4(L_(1,4)) units:

linear-1,3 (L_(1,3)) glyceryl units,

dendritic (D) glyceryl repeat units, which lead to branched and cyclicunits,

terminal-1,2 (T_(1,2)) units

and terminal-1,3 (T_(1,3)) units

In one embodiment, the polyglyceryl thickener comprises glyceryl groupsthat are glyceryl copolymer groups. By “glyceryl copolymer group” it ismeant that in addition to glyceryl units described above, the glycerylgroup includes one or more repeat units such as oxypropylene units:

Generically:

R—O

where R═C₁-C₄ linear or branched alkyl, such as —CH₂CH₂—, —CH(CH₃)CH₂—,and —CH₂CH₂CH₂—, that originate from reacting optional co-monomers (suchas ethylene carbonate, 1,2-propylene carbonate, and 1,3-propylenecarbonate) in the formation of the polyglyceryl thickeners. Furthermore,one or more of the glyceryl groups may include C₂-C₄ acyl glyceryl unitssuch as acetyl glyceryl units:

and C₁-C₄ alkyl glyceryl units, such as methyl glyceryl ether units:

According to certain preferred embodiments, the polyglycerylcompositions of the present invention have an average degree of glycerylpolymerization (DP_(g)) greater than 3. Those skilled in the art willrecognize that “average degree of glyceryl polymerization” means thenumber of glyceryl units per mole of polyglyceryl thickener on a numberaverage basis. In certain preferred embodiments, the average degree ofglyceryl polymerization is from about 4 to about 100 glyceryl repeatunits, preferably from about 4 to about 50 glyceryl repeat units, morepreferably from about 4 to about 25 glyceryl repeat units, even morepreferably from about 4 to about 15 glyceryl repeat units. In certainother preferred embodiments, the average degree of glycerylpolymerization is greater than 3 to about 11. The DP_(g) of apolyglyceryl composition is calculated in accord with the presentinvention using nuclear magnetic resonance (NMR) techniques in accordwith the Average Degree of Glyceryl Polymerization Measurement Proceduredescribed herein below.

As discussed above, each of the one or more of the (poly)glyceryl groupsare linked to the node structure by a primary linking group (L). By“linked to the node structure by a primary linking group,” it is meantthat the (poly)glyceryl group is directly linked to the node structurewith only a primary linking (functional) group therebetween. The primarylinking group may be, for example, the functional moieties that whenlinked to at least two carbon atoms form ethers, esters, carbamates(urethanes), amines, amides, ketones, carbonates, thioethers,thioesters, dithioesters, xanthates. That is, as will be understood byone of skill in the art, each primary linking group may be selectedfrom: —O—, —C(O)O—, —N(H)C(O)O—, —N(R)₂—, —N(R)C(O)—, —C(O)—, —OC(O)O—,—S—, —C(S)O—, —C(S)S—, —OC(S)S—, where each R is independently H ormethyl. According to certain preferred embodiments, the primary linkinggroup is —O—, amine, or carbamate.

In certain embodiments, the primary linking group is derived from thenucleophilic groups of the polynucleophile that was used in the processof making the polyglyceryl thickener. For example, if a polynucleophilebearing hydroxyl groups is reacted with glycerol carbonate then theresulting node structure will be substituted with (poly)glyceryl groupscovalently linked to the node by primary linking groups that are etherbonds (i.e. the linking group is —O—). As one skilled in the art wouldreadily understand, in embodiments in which the number of glyceryl unitsis larger than the number of (poly)glyceryl groups, certain glycerylunits present in the polyglyceryl thickener, rather than bonded to thenode structure, are, for example, bonded to neighboring glyceryl units.

The polyglyceryl materials further include one or more terminalhydrophobic moieties (Hphob). By “hydrophobic moieties,” is it meantnonpolar moieties that contains at least one of the following: (a) acarbon-carbon chain of at least six carbons in which none of the sixcarbons is a carbonyl carbon or has a hydrophilic moiety bonded directlyto it; (b) three or more alkyl siloxy groups (—[Si(R)₂—O]—); and/or (c)three or more oxypropylene groups in sequence. A hydrophobic moiety maybe, or include, linear, cyclic, aromatic, saturated or unsaturatedgroups. Preferred hydrophobic moieties include 9 or more carbon atoms,more preferably from 11 to 30 carbon atoms, even more preferably from 15to 26 carbon atoms, and most preferably from 17 to 24 carbon atoms.

Other examples of hydrophobic moieties include groups such aspoly(oxypropylene), poly(oxybutylene), poly(dimethylsiloxane), andfluorinated hydrocarbon groups containing a carbon chain of at least sixcarbons in which none of the six carbons has a hydrophilic moiety bondeddirectly to it, and the like.

Some specific examples of hydrophobic moieties include linear orbranched, saturated or unsaturated alkyl moieties, e.g. linear orbranched, saturated or unsaturated C₁₀-C₃₀ alkyl, such as decyl,undecyl, dodecyl (lauryl), tridecyl, tetradecyl (myristyl), pentadecyl,hexadecyl (cetyl, palmityl), heptadecyl, heptadecenyl, hepta-8-decenyl,hepta-8,11-decenyl, octadecyl (stearyl), nonadecyl, eicosanyl,henicosen-12-yl, henicosanyl, docosanyl (behenyl), and the like. Certainpreferred hydrophobic moieties include heptadecyl, heptadecenyl,hepta-8-decenyl, hepta-8,11-decenyl and the like.

Each terminal hydrophobic moiety of a polyglyceryl material of thepresent invention may be bound either to the node structure by a primarylinking functional group (L′) or to a (poly)glyceryl group by asecondary linking group (L″). Any suitable and preferred moiety asdescribed above for primary linking group (L) may also be suitableand/or preferred as a primary linking group (L′) or secondary linkinggroup (L″).

In certain embodiments, the primary linking group is derived from thenucleophilic groups of the polynucleophile that were consumed in theprocess of bonding the hydrophobic moiety to the polynucleophile. Forexample, if a polynucleophile bearing hydroxyl groups (i.e. a polyol) isreacted with fatty acids under condensation reaction conditions, thenthe resulting node structure will be substituted with hydrophobicmoieties covalently linked to the node structure by primary linkinggroups that are ester functional groups (—C(O)—). Alternatively, theprimary linking functional group may be derived from a difunctionalreagent used to covalently bind the hydrophobic moiety to thepolynucleophilic node. For example, if a polynucleophile bearinghydroxyl groups (i.e. a polyol) is reacted with a diisocyanate, followedby reaction with a fatty alcohol, then the resulting node structure willbe substituted with hydrophobic moieties covalently linked to the nodestructure by primary linking groups that are carbamate (urethane)functional groups.

Preferably, polyglyceryl materials of the present invention aresufficiently substituted with hydrophobic moieties such that thepolyglyceryl compositions have an average number of hydrophobic moietiesper primary linking group of about 0.35 or greater. By averagehydrophobic moieties per primary linking group, it is meant the quotientof the average number of hydrophobic moieties divided by (the sum ofaverage number of primary linking groups (L) and (L′)) present in thepolyglyceryl composition. In certain embodiments, the polyglycerylcomposition has from about 0.35 average hydrophobic moieties per primarylinking group, to about 0.55 average hydrophobic moieties per primarylinking group. Those of skill in the art will recognize that certainpolynucleophiles and/or starting materials of the formulaNode-(L′-Hphob)_(h) may be commercially available as a mixture of mono-,di-, and/or tri-hydrophobically-substituted species. Thus the averagenumber of hydrophobic moieties per linking group may be represented by anon-integer average value. For the purposes of clarity, the followingexample calculation is provided: for example, for a nominal sorbitandioleate ester comprising 75 mol % disubstituted sorbitan and 25 mol %monosubstituted sorbitan, the average degree hydrophobic substitution(i.e. average degree of esterification) would be equal to2(0.75)+1(0.25)=1.75 hydrophobic moieties per molecule. Since thesorbitan node bears four possible primary linking groups, the averagenumber of hydrophobic moieties per primary linking group is equal to1.75/4=0.44.

In certain embodiments, on average, the polyglyceryl material issufficiently substituted with hydrophobic moieties such that thepolyglyceryl material has about 1.5 or more hydrophobic moieties permolecule, preferably from about 1.5 to about 2.2 hydrophobic moietiesper molecule. For example, in the example calculation above thepolyglyceryl sorbitan dioleate would have 1.75 hydrophobic moieties permolecule.

While a variety of structures have been described for polyglycerylthickeners of the present invention have been described, examples ofparticularly suitable polyglyceryl thickeners include those comprisingcompounds of the formulae:

wherein R₁-R₄ are each independently either -L′-Hphob or -L-(G),provided that the thickener has on average about 1.5 or more -L′-Hphobper molecule. Such compounds are preferably derived from methyl glucose.

wherein R₁-R₄ are each independently either -L′-Hphob or -L-(G),provided that the thickener has on average about 1.5 or more -L′-Hphobper molecule. Such compounds are preferably derived from sorbitan.

wherein R₁-R₅ are each independently either -L′-Hphob or -L-(G),provided that the thickener has on average about 1.5 or more -L′-Hphobper molecule. Such compounds are preferably derived from triglycerol.

wherein R₁-R₄ are each independently either -L′-Hphob or -L-(G),provided that the thickener has on average about 1.5 or more -L′-Hphobper molecule. Such compounds are preferably derived frompentaerythritol.

wherein R₁-R₈ are each independently either -L′-Hphob or -L-(G),provided that the thickener has on average about 1.5 or more -L′-Hphobper molecule. Such compounds are preferably derived from sucrose.

wherein R₁-R₄ are each independently either -L′-Hphob or -L-(G),provided that the thickener has on average about 1.5 or more -L′-Hphobper molecule. Such compounds are preferably derived fromN,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine

According to certain preferred embodiments, polyglyceryl materials ofthe present invention derived from methyl glucose comprise polyglycerylmethyl glucose dioleate, the idealized structure for which is shownbelow:

wherein, with reference to formula I,

-   -   (a) x=2, as there are two (poly)glyceryl groups [G]:

-   -   (b) h=2, as there are two hydrophobic moieties [Hphob], both of        which are C₁₇ hydrophobes, specifically 8-heptadecenyl:

-   -   (c) the node (Z) structure is a methyl glucose remnant:

-   -   (d) residual nucleophilic groups [Nu] are absent, thus a=0    -   (e) each primary linking group L is an ether linkage:

-   -   (f) each primary linking group L′ is an ester linkage:

-   -   (g) Hphob-L″ is absent, as such y=0. In preferred embodiments,        m+n is greater than 3, preferably from about 4 to about 100,        preferably from about 4 to about 50, more preferably from about        4 to about 25, even more preferably from about 4 to about 15,        and even more preferably greater than 3 to about 11.

According to certain preferred embodiments, polyglyceryl materials ofthe present invention derived from sorbitan comprise polyglycerylsorbitan dioleate, the idealized structure for which is shown below

wherein, with reference to formula I,

-   -   (a) x=2, as there are two (poly)glyceryl groups [G]:

-   -   (b) h=2, as there are two hydrophobic moieties [Hphob], both of        which are C₁₇ hydrophobes, specifically 8-heptadecenyl:

-   -   (c) the node structure is a 2-ethyltetrahydrofuranyl:

-   -   (d) residual nucleophilic groups [Nu] are absent, thus a=0    -   (e) each primary linking group L is an ether linkage:

-   -   (f) each primary linking group L′ is an ester linkage:

-   -   (g) Hphob-L″ is absent, as such y=0. In preferred embodiments,        m+n is greater than 3, preferably from about 4 to about 100,        preferably from about 4 to about 50, more preferably from about        4 to about 25, even more preferably from about 4 to about 1, and        even more preferably greater than 3 to about 11.

According to certain preferred embodiments, polyglyceryl materials ofthe present invention derived from triglycerol comprise polyglyceryltriglycerol dioleate, the idealized structure for which is shown below:

wherein, with reference to formula I,

-   -   (a) x=2, as there are two (poly)glyceryl groups [G]:

-   -   (b) h=2, as there are two hydrophobic moieties [Hphob], both of        which are C₁₇ hydrophobes, specifically 8-heptadecenyl:

-   -   (c) the node structure is a bis(n-propyl)-1,3-propanediol ether:

-   -   (d) there is one residual nucleophilic [Nu] (hydroxyl) group,        thus a=1

-   -   (e) each primary linking group L is an ether linkage:

-   -   (f) each primary linking group L′ is an ester linkage:

-   -   (g) Hphob-L″ is absent, as such y=0. In preferred embodiments,        m+n is greater than 3, preferably from about 4 to about 100,        preferably from about 4 to about 50, more preferably from about        4 to about 25, even more preferably from about 4 to about 1, and        even more preferably greater than 3 to about 11.

According to certain preferred embodiments, the polyglyceryl thickenercompositions of the present invention comprise at least 50 mol % ofpolyglyceryl compounds having two hydrophobic groups, (e.g. withreference to Formula I, wherein h=2). In certain preferred embodiments,the polyglyceryl thickeners of the present invention comprise about 50mol % to about 100 mol % of polyglyceryl compounds having twohydrophobic groups, more preferably from about 60 mol % to about 100 mol%, more preferably from about 70 mol % to about 100 mol %, morepreferably from about 80 mol % to about 100 mol % of polyglycerylcompounds having two hydrophobic groups.

In certain particularly preferred embodiments, the polyglycerylthickeners of the present invention comprise at least 50 mol %, morepreferably about 50 mol % to 100%, more preferably from about 70 mol %to about 100 mol %, more preferably from about 80 mol % to about 100 mol% of polyglyceryl polyol dioleate (e.g. polyglyceryl methyl glucosedioleate, polyglyceryl sorbitan dioleate, and the like).

According to certain embodiments, for compounds of Formula I wherein Zis a polynucleophile remnant derived from sorbitan, then either: (a)x=2, h=2, a=0, y=0, and the compound has a degree of glycerylpolymerization of from greater than 3 to about 11, or (b) x is from 1 to3, h=1, a is from 0 to 2, y is from 1 to 3, and x+h+a+y=4.

Methods of Making Polyglyceryl Thickeners

Various synthetic routes are suitable for making polyglyceryl thickenersof the present invention. In one embodiment, the polyglyceryl thickeneris prepared via the base-catalyzed ring-opening addition polymerizationof the monomers and optional comonomers. The (co)polymerization may beperformed, for example, by first providing a polymerization initiator,e.g., a polynucleophile that has been partially substituted withhydrophobic moieties. The polymerization initiator may be represented bythe following structure:

(Nu)_(b)-ZL′-(Hphob)]_(h)

where:

-   Z=node structure;-   Each Nu is a nucleophilic group (preferably a hydroxyl group);-   Hphob=hydrophobic moiety;-   Each L′ is a primary linking group;-   h=hydrophobic moieties per nucleophilic group (hydrophobic    substitution)-   b is the number of nucleophilic groups free for bonding with    (poly)glyceryl groups.-   Examples of suitable polymerization initiators include:

(i) glucoside diesters shown below, wherein R′ is a C₁-C₄ alkyl:

such as methyl glucose dioleate, in which R═C₁₇ (—RCO=oleoyl) andR′═CH₃.

(ii) sorbitan diesters:

such as sorbitan dioleate, in which R═C₁₇ (—RCO=oleoyl);

(iii) diglyceryl diesters:

such as diglycerol dioleate, in which R═C₁₇ (—RCO=oleoyl); and

(iv) triglyceryl diesters:

such as triglycerol dioleate, in which R═C₁₇ (—RCO=oleoyl).

In certain embodiments, the polymerization initiator is a compound ofthe above formula wherein Z is not a polynucleophile remnant derivedfrom sorbitan. In certain preferred embodiments, the polymerizationinitiator may be selected from the group consisting of glucosidediesters, diglyceryl diesters, triglyceryl diesters, and combinations oftwo or more thereof.

To prepare polyglyceryl thickeners of the present invention, varioussynthetic routes may be employed, including but not limited tocondensation polymerization of glyceryl monomers such as glycerol;ring-opening polymerization of such glyceryl monomers as glycerolcarbonate or glycidol. Glyceryl monomers suitable for ring-openingpolymerization include primary monomers, (to yield glycerol repeatunits) such as glyceryl carbonate (GC), glycidol, as well as substitutedmonomers such as glycerol carbonate C₁-C₄ monoester (preferred is acetylglycerol carbonate (AcGC)) and glycidol C₁-C₄ monoester. Furthermore,optional comonomers such as ethylene carbonate, 1,2-propylene carbonate,and 1,3-propylene carbonate may be used to yield a copolyether.Furthermore, glyceryl copolymers may also be derived via thering-opening polymerization of glycerol carbonate with other cycliccarbonate monomers, such as acetylated glycerol carbonate (AcGC) toproduce acetyl glyceryl units.

Typically, the molar ratio of initiator to monomer used in the synthesisis generally at least 1:3, more usually from 1:4 to 1:100, typically 1:4to 1:75, though more usually from 1:4 to 1:50, desirably 1:4 to 1:40 andparticularly from 1:5 to 1:30. Although the synthetic reaction appearsrobust enough to make products with average DP_(g) greater than about30, reaction rates may fall off somewhat at higher DP_(g) values, whichmay be compensated for by top up (or continuous) addition of glycerolcarbonate and/or catalyst.

To accelerate the reaction, in certain embodiments it is desirable touse a catalyst, particularly a base catalyst. Accordingly, in oneembodiment, the method of making the polyglyceryl thickener includesreacting the initiator with glyceryl monomers and optional comonomers inthe presence of a base catalyst. Suitable catalysts include alkalimetal, particularly sodium or potassium, bases, e.g. hydroxides,particularly NaOH or KOH, carbonates, particularly K₂CO₃ or Na₂CO₃,bicarbonates, particularly KHCO₃ or NaHCO₃, and alkoxides, particularlysodium or potassium lower, particularly C₁ to C₄, alkoxides, e.g. sodiumor potassium methoxide, and tertiary amines, particularly tertiaryamines including at least one tertiary nitrogen atom in a ring system,such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU),1,4-diazabicyclo[2.2.2]octane (DABCO), 4-(dimethylamino)pyridine (DMAP),7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), quinuclidine,pyrrocoline, and similar materials. Base catalyst, particularly alkalimetal hydroxide may be partially neutralized (or buffered) with acid,particularly fatty acids or a polybasic acid, such as phosphorusoxyacid, e.g. phosphoric acid, or reducing phosphorus oxyacids, such asphosphorous acid. The amount of catalyst may be from 0.5 to 25, moreusually 2 to 20, and particularly 5 to 15, mol %, based on the initiatorstarting material. Calcium methoxide, Ca(OCH₃)₂, and potassiummethoxide, KOCH₃, if used, are desirably used in an amount of from 3 to18, especially from 5 to 15 mol % based on the initiator startingmaterial, are particularly useful catalysts.

To make the compounds of the invention where the (poly)glyceryl group isa glyceryl copolymer, the synthesis may include ring-openingcopolymerization with other cyclic monomers, preferably cycliccarbonates, e.g. those derived from ethylene glycol, propylene glycoland/or 1,3-propanediol, in addition to glycerol carbonate. Theproportion of such other comonomer used will be chosen to provide thecorresponding level of copolymeric inclusion in the chains andaccordingly will typically be less than 75, more usually less than 50and generally less than 25 mol % of the total carbonate used in thesynthesis. The invention further includes a method of making a mixedpoly(alkyleneoxy)/polyglycerol ether in which the initiator is reactedwith glycerol carbonate and at least one other cyclic carbonate,particularly in the presence of a base catalyst.

The relative proportions of glyceryl and other units in the glycerylcopolymer can readily be determined by controlling how the monomers aresupplied to the reaction. Thus, random (statistical) copolymers can bemade by supplying a mixture of monomers to the reaction; blockcopolymers by substantially completing reaction with one monomer beforeanother is added; taper block copolymers by adding the another monomerlater than but before complete reaction of a first carbonate reagent.Sequential block, block random, and similar types of copolymeric chainscan be made by combinations or ready variations on the above reactionsequences. In one preferred embodiment, acetylated glyceryl carbonate ispolymerized first off of the initiator, followed by subsequentpolymerization of glyceryl carbonate.

In addition to the compounds of the invention, typical synthesisreactions may generate by-products such as polyglycerol and/orpolyglyceryl copolymers in side reactions initiated by species otherthan the intended initiator, e.g. polymerization of glycerol carbonateinitiated by the free OH group of glycerol carbonate. Generally, themore monomer present in the reaction system the more likely such sidepolymerizations are to occur and consequently, aliquot or gradualaddition of monomers over the course of the reaction reduces the amountof side product made. The polyglyceryl thickener may be separated fromthe side polymerization products via any of a variety of conventionalseparation processes including, for example, decanting, fractionation,centrifugation, and/or solvent extraction.

The synthesis reactions will be generally be carried out in a batchmode, typically by mixing the reagents in a suitable vessel and allowingthem to react, usually under stirring for a suitable time. Freshreagent, particularly glycerol carbonate, and/or catalyst may be addedoccasionally, at multiple intervals or continuously during the reaction(semi-batch operation). It is also possible to use continuous orsemicontinuous reaction modes if desired.

Where the initiator and monomer(s) are immiscible, at the start of thereaction, the reactants form a two-phase liquid system. As the polyether(e.g., glyceryl and optional other units) chain of the etherifiedinitiator grows, the polyethers become increasingly miscible with themonomer(s). Thus, the products and to an extent the intermediates willtend to act to compatibilize the starting materials, but when thetransition to a single phase system occurs will depend on the reagentsused. Reaction between components (generally) in different phases willbe slower than when they are in one phase. The degree of compatibilityof the intermediates may influence the relative speed of reaction asagainst chain length and thus influence the distribution of chainlengths in the final product. In some cases, a single phase liquidsystem will not form, giving rise to two different reaction products(one from each phase) that may be separated and utilized accordingly. Inthese cases, the reaction parameters may be adjusted accordingly tofavor the formation of the desired product and minimize formation of theaccompanying by product. For example, in a two-phase reaction productresulting from the reaction of methyl glucose dioleate with glycerolcarbonate, one phase may comprise polyglyceryl methyl glucose dioleatewith a high DPg, whereas the second phase may comprise a polyglycerylmethyl glucose dioleate with a low DPg. The two phases may be separatedand collected via any of a variety of conventional separation processesincluding, for example, decanting, fractionation, centrifugation, and/orsolvent extraction.

Typically, the reactions to make the compounds of the invention can becarried out without the need for a solvent or diluent, particularly asthis will avoid any problem in isolating the desired product. However,if desired, the physical immiscibility of the starting materials may beavoided by the use of suitable inert reaction medium, solvent ordiluent; however, the reaction is preferably conducted in the bulk.Suitable solvents are liquids which remain thermally stable and areinert to the reagents and products. Any solvent used will either have arelatively low vapor pressure at the reaction temperature or thereaction will be conducted under suitable containment or refluxarrangements. Suitable examples of solvents/diluents include dimethylisosorbide, dimethylformamide, dimethylsulfoxide, and ethylene glycoland diethylene glycol diethers, e.g. dimethyl, diethyl, or dibutylethers.

Solvent and/or diluent may be included with the resulting polyglycerylthickener, either by leaving reaction solvent/diluent in the product orby subsequent addition, to reduce product viscosity for transport,storage and/or subsequent use. Suitable solvents/diluents for thispurpose include those mentioned above as well as glycerol carbonate(when its reactivity does not interfere with downstream product use),glycerol or, and particularly, monopropylene glycol because this maygive the additional benefit of improving the molecular packing of thepolyglycerol ether products at the phase interface in end useformulations. Typically such solvents/diluents will be used in amountsto give formulations having from 50 to 90, more usually 60 to 80 andparticularly about 70,% by weight of the product.

The reaction temperature may be superambient, such as at least 100° C.and more usually at least 150° C. and can range up to 220° C., with therange 170 to 200° C. being generally suitable.

Typically, the reagents used to make the compounds of the inventionremain liquids of low vapor pressure at reaction temperatures, so thereaction can be conveniently carried out at ambient pressure thoughmoderately superambient pressure may be used if desired. It is unlikelythat it will be desirable to use subambient pressure, but by choosingsuitable involatile reagents it may be possible to carry the reactionout at moderately subambient pressure.

It is preferential to apply subambient pressure (i.e. vacuum) to theinitiator during initial heating to degas and dry the initiator, asentrained oxygen will lead to discoloration of the product, andentrained water will lead to spontaneous initiation of the monomers,resulting in (co)polymers without the Node(Hphob)_(h) functionality. Itis also preferential to apply subambient pressure to the monomers priorto the reaction for degassing purposes.

To help avoid excessive color generation, particularly when reactinginitiators bearing unsaturated hydrophobic moieties, the synthesisreactions will usually be carried out in a largely oxygen freeatmosphere, e.g. in a nitrogen atmosphere (e.g., using a nitrogenblanket or sparge. For larger scale production, nitrogen blanketing maybe less necessary and perhaps omitted.

It may be desirable to include reducing agent in the reaction to aid incontrol of product color. Reducing agents commonly used for thispurpose, particularly in the manufacture of food or personal careproducts, can be used in this invention and examples include phosphorousacid (H₃PO₃), hypophosphorous acid (H₃PO₂) and borohydride (usually assodium borohydride). Where the reducing agent is itself an acid, e.g.phosphorous or hypophosphorous acid, it will usually be present as asalt, typically an alkali metal salt. The salt may be made in situ byreaction with base, e.g. part of the basic catalyst (where used) and inthis case care may be needed to ensure that sufficient base is presentto neutralize the reducing acid and to act as catalyst. When used, theamount of reducing agent will typically be from 0.1 to 15 mol %, moreusually 1 to 10 mol %, and particularly 2 to 7.5 mole %, based on theinitiator.

Another way of reducing product color is to include particulate carbon,particularly so-called “activated carbon”, or a bleaching earth, e.g.diatomaceous earth, in the reaction to absorb colored side products.When used, the amount of carbon will typically be from 0.5 to 2.5 weight% of the total reagents. Of course, this carbon or bleaching earth willgenerally be removed e.g. by filtration, before the products areincluded in end use formulations. Activated carbon and a reducing agentmay be used together in the reaction if desired. Further colorimprovement can be achieved by treatment of the reaction product withparticulate carbon, particularly activated carbon, or bleaching earth,typically at from 0.5 to 2.5 weight % of the product, or by bleachingthe product of the reaction, e.g. with a peroxide based bleach,generally after removal of any activated carbon or bleaching earth.

According to certain embodiments of the invention, polyglycerylthickener is used in a personal care composition. The personal carecomposition may comprise, consists of, or consist essentially of a baseand the polyglyceryl thickener. The base comprises water, surfactant,and optionally, any of various ingredients typically used in personalcare products.

Any amounts of polyglyceryl thickeners suitable to increase viscosity ofcompositions of the present invention may be used according to thepresent methods. For example, polyglyceryl thickener may be included inan amount in the personal care composition sufficient to increase theZero Shear Viscosity of the base by about 100 cP or more (when testedaccording to the Zero Shear Viscosity Test, described below). In certainpreferred embodiments, the compositions of the present inventioncomprise an amount of polyglyceryl thickener sufficient to increase theZero Shear Viscosity of the base by about 200 cP or more, morepreferably by about 300 cP or more, more preferably by about 500 cP ormore, more preferably by about 1000 cP or more. The increases inviscosity specified above are as when compared with a composition whichhas water substituted for the polyglyceryl thickener.

According to certain embodiments, the polyglyceryl thickener is used ina concentration from greater than about 0.1% to about 15% by weight inthe composition. Preferably, the polyglyceryl thickener is in aconcentration from about 0.1to about 10%, more preferably from about0.1% to about 5%, even more preferably from about 0.2% to about 4%, evenmore preferably from about 0.5% to about 4%, and most preferably fromabout 1% to about 4% in the composition.

Compositions useful in the present invention may also include any of avariety of surfactants. The surfactants may be anionic, zwitterionic(i.e. amphoteric or betaine), nonionic, or cationic, examples of whichare detailed below. Where applicable, chemicals are specified accordingto their International Nomenclature of Cosmetic Ingredients (INCI)names.

According to certain embodiments, suitable anionic surfactants includethose selected from the following classes of surfactants: alkylsulfates, alkyl ether sulfates, alkyl monoglyceryl ether sulfates, alkylsulfonates, alkylaryl sulfonates, alkyl sulfosuccinates, alkyl ethersulfosuccinates, alkyl sulfosuccinamates, alkyl amidosulfosuccinates,alkyl carboxylates, alkyl amidoethercarboxylates, alkyl succinates,fatty acyl sarcosinates, fatty acyl amino acids, fatty acyl taurates,fatty alkyl sulfoacetates, alkyl phosphates, and mixtures of two or morethereof. Examples of certain preferred anionic surfactants include:

where R═C₈-C₂₄ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof and M⁺=monovalent cation. Examples include SodiumLauryl Sulfate (R═C₁₂ alkyl, M⁺=Na⁺), Ammonium Lauryl Sulfate (R═C₁₂alkyl, M⁺=NH₃ ⁺), and Sodium Coco-Sulfate (R=coconut alkyl, M⁺=Na⁺);

where R═C₈-C₂₄ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof, n=1-12, and M⁺=monovalent cation. Examples includeSodium Laureth Sulfate (R═C₁₂ alkyl, M⁺=Na⁺, n=1-3), Ammonium LaurethSulfate (R═C₁₂ alkyl, M⁺=NH₃ ⁺, n=1-3), and Sodium Trideceth Sulfate(R═C₁₃ alkyl, M⁺=Na⁺, n=1-4);

where R═C₈-C₂₄ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof and M⁺=monovalent cation. Examples include SodiumCocomonoglyceride Sulfate (RCO=coco acyl, M⁺=Na⁺) and AmmoniumCocomonoglyceride Sulfate (RCO=coco acyl, M⁺=NH₃ ⁺);

where R═C₈-C₂₄ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof and M⁺=monovalent cation. Examples include SodiumLaurate (R═C₁₁H₂₃, M⁺=Na⁺) and Potassium Myristate (R═C₁₃H₂₇, M⁺=K⁺);

where R═C₈-C₂₄ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof, n=1-20, and M⁺=monovalent cation. Examples includeSodium Laureth-13 Carboxylate (R═C₁₂ alkyl, M⁺=Na⁺, n=13), and SodiumLaureth-3 Carboxylate (R═C₁₂ alkyl, M⁺=Na⁺, n=3);Alpha olefin sulfonates prepared by sulfonation of long chain alphaolefins. Alpha olefin sulfonates consist of mixtures of alkenesulfonates,

where R═C₈-C₁₈ alkyl or mixtures thereof and M⁺=monovalent cation, andhydroxyalkyl sulfonates,

where R═C₄-C₁₈ alkyl or mixtures thereof and M⁺=monovalent cation.Examples include Sodium C12-14 Olefin Sulfonate (R═C₈-C₁₀ alkyl, M⁺=Na⁺)and Sodium C14-16 Olefin Sulfonate (R═C₁₀-C₁₂ alkyl, M⁺=Na⁺);

where R═C₈-C₂₄ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof and M⁺=monovalent cation. Examples include SodiumC13-17 Alkane Sulfonate (R═C₁₃-C₁₇ alkyl, M⁺=Na⁺) and Sodium C14-17Alkyl Sec Sulfonate (R═C₁₄-C₁₇ alkyl, M⁺=Na⁺);

where R═C₆-C₁₈ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof and M⁺=monovalent cation. Examples include SodiumDeceylbenzenesulfonate (R═C₁₀ alkyl, M⁺=Na⁺) and AmmoniumDodecylbenzensulfonate (R═C₁₂ alkyl, M⁺=NH₃ ⁺);

where R═C₈-C₂₄ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof and M⁺=monovalent cation, such as Sodium CocoglycerylEther Sulfonate (R=coco alkyl, M⁺=Na⁺);

Where R═C₈-C₂₀ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof and M⁺=monovalent cation, such as Disodium LaurylSulfosuccinate (R=lauryl, M⁺=Na⁺).

Where R═C₈-C₂₀ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof, n=1-12, and M⁺=monovalent cation, such as DisodiumLaureth Sulfosuccinate (R=lauryl, n=1-4, and M⁺=Na⁺)

Where R═C₆-C₂₀ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof and M⁺=monovalent cation, such as Diethylhexyl SodiumSulfosuccinate (R=2-ethylhexyl, M⁺=Na⁺).

Where R═C₈-C₂₀ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof, R′═C₂-C₄ alkyl (linear or branched), and M⁺=monovalentcation, such as Disodium Cocamido MIPA-Sulfosuccinate (RCO=coco acyl,R′=isopropyl, M⁺=Na⁺).

Where R═C₈-C₂₀ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof and M⁺=monovalent cation, such as Disodium StearylSulfosuccinamate (R=stearyl, C₁₈H₃₇, M⁺=Na⁺).

Where R═C₆-C₁₆ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof, R′═C₁-C₄ alkyl, and M⁺=monovalent cation, such asSodium Methyl 2-Sulfolaurate (R═C₁₀H₂₁, R′═methyl, CH₃, and M⁺=Na⁺).

Where R═C₆-C₁₆ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof, M⁺=monovalent cation, such as Disodium 2-Sulfolaurate(R═C₁₀H₂₁, M⁺=Na⁺).

Where R═C₈-C₁₈ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof, M⁺=monovalent cation, such as Sodium LaurylSulfoacetate (R=lauryl, C₁₂H₂₅, M⁺=Na⁺).

Where RCO═C₈-C₂₀ acyl (linear or branched, saturated or unsaturated) ormixtures thereof, R′═H or CH₃, M⁺=monovalent cation, such as SodiumCocoyl Isethionate (RCO=coco acyl, R′═H, M⁺=Na⁺) and Sodium LauroylMethyl Isethionate (RCO=lauroyl, R′═CH₃, M⁺=Na⁺).

Where RCO═C₈-C₂₀ acyl (linear or branched, saturated or unsaturated) ormixtures thereof, M⁺=monovalent cation, such as Sodium Lauroyl Lactylate(RCO=lauroyl, M⁺=Na⁺).

Where RCO═C₈-C₂₀ acyl (linear or branched, saturated or unsaturated) ormixtures thereof, R′═H (glycinate) or CH₃ (sarcosinate), M⁺=monovalentcation, such as Sodium Cocoyl Glycinate (RCO=coco acyl, R′═H, M⁺=Na⁺),Ammonium Cocoyl Sarcosinate (RCO=coco acyl, R′═CH₃, M⁺=NH₄ ⁺) and SodiumLauroyl Sarcosinate (RCO=lauroyl, R′═CH₃, M⁺=Na+).

Where RCO═C₈-C₂₀ acyl (linear or branched, saturated or unsaturated) ormixtures thereof, R′═H or CH₃, M⁺=monovalent cation, such as DisodiumCocoyl Glutamate (RCO=coco acyl, R′═H, M⁺=Na⁺) and Disodium LauroylGlutamate (RCO=lauroyl, R′═H, M⁺=Na⁺).

Where RCO═C₈-C₂₀ acyl (linear or branched, saturated or unsaturated) ormixtures thereof, R′═H or CH₃, M⁺=monovalent cation, such as DisodiumN-Lauroyl Aspartate (RCO=lauroyl, R′═H, M⁺=Na⁺).

Where RCO═C₆-C₂₀ acyl (linear or branched, saturated or unsaturated) ormixtures thereof, R′═H or CH₃, M⁺=monovalent cation, such as DisodiumCocoyl Glutamate (RCO=coco acyl, R′═H, M⁺=Na⁺) and Disodium LauroylGlutamate (RCO=lauroyl, R′═H, M⁺=Na+).

Where R═C₆-C₂₀ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof and M⁺=monovalent cation, such as Potassium LaurylPhosphate (R=lauryl, C₁₂H₂₅, M⁺=K⁺) and Potassium C12-13 Alkyl Phosphate(R═C₁₂-C₁₃ alkyl, M⁺=K⁺)

Anionic derivatives of alkyl polyglucosides (APGs), including: SodiumLauryl Glucoside Carboxylate, Disodium Coco-Glucoside Citrate, SodiumCoco-Glucoside Tartrate, Disodium Coco-Glucoside Sulfosuccinate, SodiumCocoglucosides Hydroxypropylsulfonate, Sodium DecylglucosidesHydroxypropylsulfonate, Sodium Laurylglucosides Hydroxypropylsulfonate,Sodium Hydroxypropylsulfonate Cocoglucoside Crosspolymer, SodiumHydroxypropylsulfonate Decylglucoside Crosspolymer, SodiumHydroxypropylsulfonate Laurylglucoside Crosspolymer; and anionicpolymeric APG derivatives, such as those described in O'Lenick, U.S.Pat. Nos. 7,507,399; 7,375,064; and 7,335,627), and combinations of twoor more thereof, and the like.

Any of a variety of amphoteric surfactants are suitable for use in thepresent invention. As used herein, the term “amphoteric” shall mean: 1)molecules that contain both acidic and basic sites such as, for example,an amino acid containing both amino (basic) and acid (e.g., carboxylicacid, acidic) functional groups; or 2) zwitterionic molecules whichpossess both positive and negative charges within the same molecule. Thecharges of the latter may be either dependent on or independent of thepH of the composition. Examples of zwitterionic materials include, butare not limited to, alkyl betaines and alkylamidoalkyl betaines. Theamphoteric surfactants are disclosed herein with a counterion. Oneskilled in the art would readily recognize that under the pH conditionsof the compositions of the present invention, the amphoteric surfactantsare either electrically neutral by virtue of having balancing positiveand negative charges, or they have counter ions such as alkali metal,alkaline earth, or ammonium counter ions. Examples of amphotericsurfactants suitable for use in the present invention include, but arenot limited to, amphocarboxylates such as alkylamphoacetates (mono ordi); alkyl betaines; alkylamidoalkyl betaines; alkylamidoalkylsultaines; alkylamphophosphates; phosphorylated imidazolines such asphosphobetaines and pyrophosphobetaines; carboxyalkyl alkyl polyamines;alkylimino-dipropionates; alkylamphoglycinates (mono or di);alkylamphoproprionates (mono or di),); N-alkyl β-aminoproprionic acids;alkylpolyamino carboxylates; and mixtures thereof Specific examplesinclude:

where R═C₈-C₂₄ alkyl (saturated or unsaturated) or mixtures thereofExamples include Coco-Betaine (R=coco alkyl), Lauryl Betaine (R=lauryl,C₁₂H₂₅), and Oleyl Betaine (R═oleyl, C₁₈H₃₅).

where R═C₈-C₂₄ alkyl (saturated or unsaturated) or mixture thereofExamples include Coco-Hydroxysultaine (R=coco alkyl) and LaurylHydroxysultaine (R=lauryl, C₁₂H₂₅).

where R═C₈-C₂₄ alkyl (saturated or unsaturated) or mixture thereofExamples include Lauryl Sultaine (R=lauryl, C₁₂H₂₅) and Coco-Sultaine(R=coco alkyl).

where RCO═C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof andx=1-4. Examples include Cocamidoethyl Betaine (RCO=coco acyl, x=2),Cocamidopropyl Betaine (RCO=coco acyl, x=3), Lauramidopropyl Betaine(RCO=lauroyl, and x=3), Myristamidopropyl Betaine (RCO=myristoyl, andx=3), Soyamidopropyl Betaine (R=soy acyl, x=3), and OleamidopropylBetaine (RCO=oleoyl, and x=3).

where RCO═C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof.Examples include Cocamidopropyl Hydroxysultaine (RCO=coco acyl, x=3),Lauramidopropyl Hydroxysultaine (RCO=lauroyl, and x=3),Myristamidopropyl Hydroxysultaine (RCO=myristoyl, and x=3), andOleamidopropyl Hydroxysultaine (RCO=oleoyl, and x=3).

where RCO═C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof.Examples include Cocamidopropyl Sultaine (RCO=coco acyl, x=3),Lauramidopropyl Sultaine (RCO=lauroyl, and x=3), MyristamidopropylSultaine (RCO=myristoyl, and x=3), Soyamidopropyl Betaine (RCO=soy acyl,x=3), and Oleamidopropyl Betaine (RCO=oleoyl, and x=3).

where R═C₆-C₂₄ alkyl (saturated or unsaturated) or mixtures thereof andM⁺=monovalent cation, such as Sodium Coco PG-Dimonium ChloridePhosphate, where R=coco alkyl and M⁺=Na⁺.

where R═C₆-C₂₄ alkyl (saturated or unsaturated) or mixtures thereof,x=1-3 or mixtures thereof, x+y=3, z=x, a=0 to 2, B═O⁻ or OM, A=Anion,and M=Cation (refer to U.S. Pat. Nos. 5,215,976; 5,286,719; 5,648,348;and 5,650,402), such as Sodium Coco PG-Dimonium Chloride Phosphate,where R=coco alkyl, x=2, B═O⁻, y=1, z=1, A=Cl⁻, a=1, and M=Na⁺.

where RCO═C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof,n=1-4, x=1-3 or mixtures thereof, x+y=3, z=x, a=0 to 2, B═O⁻ or OM,A=anion, and M=cation (refer to U.S. Pat. Nos. 5,215,976; 5,286,719;5,648,348; and 5,650,402). Examples include Cocamidopropyl PG-DimoniumChloride Phosphate (RCO=coco acyl, n=3, x=3, z=3, A=Cl⁻, B and M areabsent, y=0, and a=0) and Myristamidopropyl PG-Dimonium ChloridePhosphate (RCO=myristoyl, n=3, x=3, z=3, A=Cl⁻, B and M are absent, y=0,and a=0).

where RCO═C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof andM⁺=monovalent cation. Examples include Sodium Lauroamphoacetate(RCO=lauroyl and M⁺=Na⁺) and Sodium Cocoamphoacetate (RCO=coco acyl andM⁺=Na⁺).

where RCO═C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof andM⁺=monovalent cation. Examples include Disodium Lauroamphodiacetate(RCO=lauroyl and M=Na⁺) and Disodium Cocoamphodiacetate (RCO=coco acyland M=Na⁺).

where RCO═C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof andM⁺=monovalent cation. Examples include Sodium Lauroamphopropionate(RCO=lauroyl and M⁺=Na⁺) and Sodium Cocoamphopropionate (RCO=coco acyland M⁺=Na⁺).

where RCO═C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof andM⁺=monovalent cation. Examples include Disodium Lauroamphodipropionate(RCO=lauroyl and M⁺=Na⁺) and Disodium Cocoamphodipropionate (RCO=cocoacyl and M⁺=Na+).

where RCO═C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof andM⁺=monovalent cation, such as Sodium Lauroamphohydroxypropylsulfonate(RCO=lauroyl and M⁺=Na⁺) and Sodium Cocoamphohydroxypropylsulfonate(RCO=coco acyl and M⁺=Na⁺).

where RCO═C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof andM⁺=monovalent cation, such as Sodium Lauroampho PG-Acetate Phosphate(RCO=lauroyl and M⁺=Na⁺).

where R═C₆-C₂₄ alkyl (saturated or unsaturated) or mixtures thereof.Examples include Cocamine Oxide (R=coco alkyl) and Lauramine Oxide(RCO=lauryl).

where RCO═C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof andx=1-4. Examples include Cocamidopropylamine Oxide (RCO=coco acyl, x=3)and Lauramidopropylamine Oxide (RCO=lauroyl, x=3), and combinations oftwo or more thereof, and the like.

Any of a variety of ethoxylated nonionic surfactants are suitable foruse in the present invention. Examples of suitable nonionic surfactantsinclude, but are not limited to: fatty alcohol, fatty acid, or fattyamide ethoxylates; monoglyceride ethoxylates; sorbitan esterethoxylates; mixtures thereof; and the like. Certain preferredethoxylated nonionic surfactants include polyethyleneoxy derivatives ofpolyol esters, wherein the polyethyleneoxy derivative of polyol ester(1) is derived from (a) a fatty acid containing from about 8 to about22, and preferably from about 10 to about 14 carbon atoms, and (b) apolyol selected from sorbitol, sorbitan, glucose, a-methyl glucoside,polyglucose having an average of about 1 to about 3 glucose residues permolecule, glycerol, pentaerythritol and mixtures thereof, (2) containsan average of from about 10 to about 120, and preferably about 20 toabout 80 ethyleneoxy units; and (3) has an average of about 1 to about 3fatty acid residues per mole of polyethyleneoxy derivative of polyolester. Examples of such preferred polyethyleneoxy derivatives of polyolesters include, but are not limited to PEG-80 Sorbitan Laurate andPolysorbate 20.

While the compositions may comprise ethoxylated materials as describedabove in accord with certain embodiments, according to certain otherembodiments, the compositions of the present invention are substantiallyfree of ethoxylated materials. As used herein, the term “substantiallyfree of ethoxylated materials” means a composition that comprises lessthan 1% by weight of total ethoxylated materials. In preferredembodiments, compositions that are substantially free of ethoxylatedmaterials comprise less than 0.5%, more preferably less than 0.1%, andeven more preferable are free of, ethoxylated materials.

As used herein, the term “ethoxylated material” means a materialcomprising one or more moieties derived from or prepared by thering-opening oligomerization or polymerization of ethylene oxide and/orcomprising one or more oxyethylene (—CH₂CH₂O—) moieties. Examples ofethoxylated materials include, but are not limited to, ethoxylatedsurfactants, emulsifiers, solubilizers, rheology modifiers, conditioningagents, preservatives, and the like, such as, for example anionicsurfactants: polyoxyethylene alkyl ether sulfates (a.k.a. alkyl ethersulfates), polyoxyethylene alkyl ether carboxylates (a.k.a. alkyl ethercarboxylates), polyoxyethylene alkyl ether sulfosuccinate esters;nonionic surfactants, emulsifiers, and solubilizers: polyoxyethylenealkyl ethers and esters, polysorbates, ethoxylated sorbitan fatty acidesters, ethoxylated glyceryl fatty acid esters, poloxamers; rheologymodifiers: polyoxyethylene esters (e.g. PEG-150 Distearate),ethyoxylated alkyl glucoside esters (e.g. PEG-120 Methyl GlucoseTrioleate), acrylic copolymers with ethoxylated associativemacromonomers (e.g. Acrylates/Steareth-20 Methacrylate Copolymer),ethoxylated cellulose ethers (e.g. Hydroxyethylcellulose); conditioningagents: ethoxylated polyquaterniums (e.g. Polyquaternium-10); and thelike.

Any of a variety of non-ethoxylated nonionic surfactants are alsosuitable for use in the present invention. Examples of suitablenon-ethoxylated nonionic surfactants include alkyl polyglucosides, alkylpolypentosides, polyglyceryl esters, polyglyceryl ethers, polyglycerylsorbitan fatty acid esters, sucrose esters, and sorbitan esters, andcombinations of two or more thereof and the like. Certain preferrednon-ethoxylated nonionic surfactants include C₈-C₁₈ polyglycerylmonoesters (e.g. polyglyceryl-4 caprylate/caprate, polyglyceryl-10caprylate/caprate, polyglyceryl-4 caprate, polyglyceryl-10 caprate,polyglyceryl-4 laurate, polyglyceryl-5 laurate, polyglyceryl-6 laurate,polyglyceryl-10 laurate, polyglyceryl-10 cocoate, polyglyceryl-10myristate, polyglyceryl-10 oleate, polyglyceryl-10 stearate, andcombinations of two or more thereof) and c₈-c₁₈ polyglyceryl monoethers(e.g. polyglyceryl-4 lauryl ether, polyglyceryl-10 lauryl ether)

Another class of suitable nonionic surfactants includes long chain alkylglucosides or polyglucosides, which are the condensation products of (a)a long chain alcohol containing from about 6 to about 22, and preferablyfrom about 8 to about 14 carbon atoms, with (b) glucose or aglucose-containing polymer. Preferred alkyl glucosides comprise fromabout 1 to about 6 glucose residues per molecule of alkyl glucoside. Apreferred glucoside is Decyl Glucoside, which is the condensationproduct of decyl alcohol with a glucose polymer and is availablecommercially from Cognis Corporation of Ambler, Pa. under the tradename, “Plantaren 2000N UP.” Other examples include Coco-Glucoside andLauryl Glucoside.

The compositions of the present invention may comprise any of a varietyof additional other ingredients used conventionally inhealthcare/personal care compositions (“personal care components”).These other ingredients nonexclusively include one or more, pearlescentor opacifying agents, thickening agents, emollients, secondaryconditioners, humectants, chelating agents, actives, exfoliants, andadditives which enhance the appearance, feel and fragrance of thecompositions, such as colorants, fragrances, preservatives, pH adjustingagents, and the like.

Compositions useful in the present invention may also include any of avariety of conventional thickening agents. Examples of such thickeningagents include: electrolytes (e.g. Sodium Chloride, Ammonium Chloride,Magnesium Chloride); naturally-derived polysaccharides (e.g. XanthanGum, Dehydroxanthan Gum, Cyamopsis Tetragonoloba (Guar) Gum, Cassia Gum,Chondrus Crispus (Carrageenan) Gum, Alginic Acid and alginate gums(Algin, Calcium Alginate, etc.), Gellan Gum, Pectin, MicrocrystallineCellulose); derivatives of natural polysaccharides (e.g.Hydroxyethylcellulose, Ethyl Hydroxyethylcellulose, CetylHydroxyethylcellulose, Methylcellulose, Hydroxypropylcellulose, SodiumCarboxymethylcellulose, Hydroxypropyl Methylcellulose, HydroxypropylGuar, Carboxymethyl Hydroxypropyl Guar, C18-22 HydroxylalkylHydroxypropyl Guar); alkali-swellable emulsion (ASE) polymers (e.g.Acrylates Copolymer, available under the trade name Carbopol® AQUA SF-1from Noveon Consumer Specialties, Brecksville, Ohio, and AcrylatesCopolymer available under the trade name Aculyn™ 33 from Dow PersonalCare, Spring House, Pa.); hydrophobically-modified alkali-swellableemulsion (HASE) polymers (e.g. Acrylates/Steareth-20 MethacrylateCopolymer, Acrylates/Steareth-20 Methacrylate Crosspolymer, andAcrylates/Ceteth-20 Itaconate Copolymer); hydrophobically-modifiedacid-swellable emulsion polymers (e.g. Acrylates/Aminoacrylates/C10-30Alkyl PEG-20 Itaconate Copolymer and Polyacrylate-1 Crosspolymer);hydrophobically-modified acrylate crosspolymers, such as AcrylatesC10-30 Alkyl Acrylates Crosspolymer, available under the trade nameCarbopol® 1382 from Lubrizol Corp., Brecksville, Ohio; and hydrophobicnon-ethoxylated micellar thickeners (e.g. Glyceryl Oleate, CocamideMIPA, Lauryl Lactyl Lactate, or Sorbitan Sesquicaprylate).

Any of a variety of skin and/or hair conditioning agents are suitablefor use in this invention. Examples include: cationic surfactants (e.g.Cetrimonium Chloride, Stearamidopropyl Dimethylamine, DistearyldimoniumChloride, Lauryl Methyl Gluceth-10 Hydroxypropyldimonium Chloride);cationic polymers (e.g. cationically-modified polysaccharides, includingPolyquaternium-10, Polyquaternium-24, Polyquaternium-67, StarchHydroxypropyltrimonium Chloride, Guar Hydroxypropyltrimonium Chloride,and Hydroxypropyl Guar Hydroxypropyltrimonium Chloride, and cationicpolymers derived from the (co)polymerization ofethylenically-unsaturated cationic monomers with optional hydrophilicmonomers, including Polyquaternium-5, Polyquaternium-6,Polyquaternium-7, Polyquaternium-11, Polyquaternium-14,Polyquaternium-15, Polyquaternium-28, Polyquaternium-39,Polyquaternium-44; Polyquaternium-76); silicones and siliconederivatives (e.g. Dimethicone and derivatives thereof, such as alkyl-,polyalkyleneoxy-, cationically-, anionically-modified dimethicone(co)polymers); and emollients (e.g. Caprylic/Capric Triglycerides,Mineral Oil, Petrolatum, Di-PPG-2 Myreth-10 Adipate).

Any of a variety of humectants, which are capable of providingmoisturization and conditioning properties to the personal cleansingcomposition, are suitable for use in the present invention. Examples ofsuitable humectants nonexclusively include polyols, such as Glycerin,Propylene Glycol, 1,3-Propanediol, Butylene Glycol, Hexylene Glycol,polyglycerins (e.g. Polyglycerin-3, Polyglyceryn-6, Polyglycerin-10),polyethylene glycols (PEGs), and polyoxyethylene ethers of a-methylglucose, such as Methyl Gluceth-10 and Methyl Gluceth-20.

Examples of suitable chelating agents include those which are capable ofprotecting and preserving the compositions of this invention.Preferably, the chelating agent is ethylenediamine tetraacetic acid(“EDTA”), and more preferably is Tetrasodium EDTA or TetrasodiumGlutamate Diacetate.

Suitable preservatives include, for example, organic acids, parabens(e.g. Methylparaben, Ethylparaben, Propylparaben, Butylparaben,Isobutylparaben), quaternary ammonium species (e.g. Quaternium-15),phenoxyethanol, DMDM hydantoin, Diazolidinyl Urea, Imidazolidinyl Urea,Iodopropynyl Butylcarbamate, Methylisothazolinone,Methylchloroisothizaolinone, Benzyl Alcohol, Caprylyl Glycol, DecyleneGlycol, Ethylhexylglycerin, and Gluconolactone. Preferred are organicacid preservatives that comprise at least one carboxylic acid moiety andare capable of preserving a composition of the present invention againstmicrobial contamination Examples of suitable organic acids includeBenzoic Acid and alkali metal and ammonium salts thereof (e.g. SodiumBenzoate and the like), Sorbic Acid and alkali metal and ammonium saltsthereof (e.g. Potassium Sorbate and the like), p-Anisic Acid and alkalimetal and ammonium salts thereof, Salicylic Acid and alkali metal andammonium salts thereof, and the like. In certain preferred embodiments,the organic acid preservative comprises Benzoic Acid/Sodium Benzoate,Sorbic Acid/Potassium Sorbate, or combinations thereof.

The pH of the composition may be adjusted to the appropriate value usingany number of cosmetically acceptable pH adjusters, including: alkalimetal and ammonium hydroxides (e.g. Sodium Hydroxide, PotassiumHydroxide), alkali metal and ammonium carbonates (e.g. PotassiumCarbonate), organic acids (e.g. Citric Acid, Acetic Acid, Glycolic Acid,Lactic Acid, Malic acid, Tartaric Acid), and inorganic acids (e.g.Hydrochloric Acid, Phosphoric Acid), and the like.

The polyglyceryl thickener, optional monomeric surfactants and optionalother components of the composition may be combined according to thepresent invention via any conventional methods of combining two or morefluids or solids. For example, one or more compositions comprising,consisting essentially of, or consisting of at least one polyglycerylthickener and one or more compositions comprising, consistingessentially of, or consisting of water, monomeric surfactants orsuitable ingredients may be combined by pouring, mixing, addingdropwise, pipetting, pumping, and the like, one of the compositionscomprising the polyglyceryl thickener into or with the other in anyorder using any conventional equipment such as a mechanically stirredpropeller, paddle, and the like.

The methods of the present invention may further comprise any of avariety of steps for mixing or introducing one or more of the optionalcomponents described hereinabove with or into a composition comprising apolyglyceryl thickener either before, after, or simultaneously with thecombining step described above. While in certain embodiments, the orderof mixing is not critical, it is preferable, in other embodiments, topre-blend certain components, such as the fragrance and the nonionicsurfactant before adding such components into a composition comprisingthe polyglyceryl thickener.

Applicants have recognized that n accord with certain embodiments, thecompositions of the present invention are suitable for generatingdesirable amounts of foam. According to certain embodiments, thecompositions of the present invention exhibit foam values of about 75 mLor greater as measured in accord with the Formulation Foam Test.According to certain preferred embodiments, the compositions of thepresent invention exhibit foam values of about 100 mL or greater, morepreferably about 125 mL or greater, and even more preferably about 150mL or greater as measured in accord with the Formulation Foam Test.

The compositions useful in the present invention involve formulationssuitable for administering to the target tissues, such as mammalian skinsuch as human skin. In one embodiment, the composition comprises apolyglyceryl thickener and a base, preferably a cosmetically-acceptablebase. As used herein, the term “cosmetically-acceptable base” means abase that is suitable for use in contact with the skin without unduetoxicity, incompatibility, instability, irritation, allergic response,and the like. This term is not intended to limit the base for use solelyas a cosmetic (e.g., the ingredient/product can be used as apharmaceutical).

The compositions may be made into a wide variety of product types thatinclude but are not limited to cleansing liquid washes, gels, sticks,sprays, solid bars, shampoos, pastes, foams, powders, mousses, shavingcreams, wipes, patches, wound dressing and adhesive bandages, hydrogels,films and make-up such as foundations, mascaras, and lipsticks. Theseproduct types may comprise several types of cosmetically-acceptablecarriers including, but not limited to solutions, emulsions (includingmicroemulsions and nanoemulsions), suspensions, gels, and solids. Thefollowing are non-limitative examples of such carriers. Other carrierscan be formulated by those of ordinary skill in the art.

The compositions useful in the present invention can be formulated assolutions. Solutions typically include an aqueous or organic solvent(e.g., from about 50% to about 99.99% or from about 90% to about 99% ofa cosmetically acceptable aqueous or organic solvent). Examples ofsuitable organic solvents include: polyglycerols, propylene glycol,polyethylene glycol (200, 600), polypropylene glycol (425, 2025),glycerol, 1,2,4-butanetriol, sorbitol esters, 1,2,6-hexanetriol,ethanol, and mixtures thereof In certain preferred embodiments, thecompositions of the present invention are aqueous solutions comprisingfrom about 50% to about 99% by weight of water.

According to certain embodiments, compositions useful in the subjectinvention may be formulated as a solution comprising an emollient. Suchcompositions preferably contain from about 2% to about 50% of anemollient(s). As used herein, “emollients” refer to materials used forthe prevention or relief of dryness, as well as for the protection ofthe skin. A wide variety of suitable emollients are known and may beused herein. A lotion can be made from such a solution. Lotionstypically comprise from about 1% to about 20% (e.g., from about 5% toabout 10%) of an emollient(s) and from about 50% to about 90% (e.g.,from about 60% to about 80%) of water.

The compositions of this invention can also be formulated as a gel(e.g., an aqueous, alcohol, alcohol/water, or oil gel using a suitablegelling agent(s)). Suitable gelling agents for aqueous and/or alcoholicgels include, but are not limited to, natural gums, acrylic acid andacrylate polymers and copolymers, and cellulose derivatives (e.g.,hydroxymethyl cellulose and hydroxypropyl cellulose). Suitable gellingagents for oils (such as mineral oil) include, but are not limited to,hydrogenated butylene/ethylene/styrene copolymer and hydrogenatedethylene/propylene/styrene copolymer. Such gels typically comprisesbetween about 0.1% and 5%, by weight, of such gelling agents.

The present compositions may be of varying phase compositions, but arepreferably aqueous solutions or otherwise include an exterior aqueousphase (e.g., aqueous phase is the most exterior phase of thecomposition). As such, compositions of the present invention may beformulated to be oil-in-water emulsions that are shelf-stable in thatthe emulsion does not lose phase stability or “break” when kept atstandard conditions (22 degrees Celsius, 50% relative humidity) for aweek or more after it is made.

In certain embodiments, the compositions produced via the presentinvention are preferably used as or in healthcare products for treatingor cleansing at least a portion of a mammalian body, for example, thehuman body. Examples of certain preferred personal care products includevarious products suitable for application to the skin, hair, oral and/orperineal region of the body, such as shampoos, hand, face, and/or bodywashes, bath additives, gels, lotions, creams, and the like. Asdiscussed above, applicants have discovered unexpectedly that theinstant methods provide personal care products having reduced irritationto the skin and/or eyes and, in certain embodiments one or more ofdesirable properties such as flash foaming characteristics, rheology,and functionality, even at high surfactant concentrations. Such productsmay further include a substrate onto which a composition is applied foruse on the body. Examples of suitable substrates include a wipe, pouf,sponge, and the like as well as absorbent articles, such as a bandage,sanitary napkin, tampon, and the like.

The present invention provides methods of treating and/or cleansing thehuman body comprising contacting at least a portion of the body with acomposition of the present invention. Certain preferred methodscomprising contacting mammalian skin, hair and/or vaginal region with acomposition of the present invention to cleanse such region and/or treatsuch region for any of a variety of conditions including, but notlimited to, acne, wrinkles, dermatitis, dryness, muscle pain, itch, andthe like. In certain preferred embodiments, the contacting stepcomprises applying a composition of the present invention to human skin,hair or vaginal region. The cleansing methods of the present inventionmay further comprise any of a variety of additional, optional stepsassociated conventionally with cleansing hair and skin including, forexample, lathering, rinsing steps, and the like.

EXAMPLES

The following Test Methods and Procedures were used:

Average Degree of Glyceryl Polymerization Measurement Procedure

The average degree of glyceryl polymerization DP_(g) for a subjectpolyglyceryl thickener was obtained using NMR techniques as follows: ¹HNMR spectra were obtained in deuterated dimethyl sulfoxide (DMSO-D6) ora mixture of DMSO-D6 and deuterated chloroform (CDCl₃) at concentrationsbetween 30-40 mg/mL using a Jeol spectrometer operating at 500 MHz (JeolLtd., Tokyo, Japan) for: (a) the hydrophobically-substitutedpolynucleophile (polymerization initiator) from which the polyglycerylthickener is derived, i.e. (Nu)_(b)-Node-(L′-Hphob)_(h) as describedabove; (b) polyglycerin-10 (Natrulon H-10 available from Lonza Group);and (c) the subject polyglyceryl thickener for which DP_(g) is to bedetermined Based on the reference spectra (a) and (b), the peaksassociated with the five characteristic carbon-bonded (i.e.methylene/methine) protons of glyceryl units and the peaks associatedwith a selected number of characteristic protons of theNode-(L′-Hphob)_(h) moiety are assigned. The area under the curve forpeaks associated with the five glyceryl unit protons in spectrum (c) iscalculated (minus any contribution from overlapping protons ofNode-(L′-Hphob)_(h)) and divided by five to normalize for thecorresponding number of protons per mole of glyceryl unit. The areaunder the curve for peaks associated with the selected characteristicprotons of the Node-(L′-Hphob)_(h) in spectrum (c) is calculated anddivided by the total number of characteristic protons to normalize forthe number of such protons per mole of Node-(L′-Hphob)_(h). The DP_(g)of the polyglyceryl thickener is then calculated as: [normalized area ofpolyglyceryl units]/[normalized area of Node-(L′-Hphob)_(h)]. The DPgsthus calculated are generally accurate to within ±5-10%

For the purpose of clarity the following example calculation is providedfor a polyglyceryl thickener comprising polyglyceryl methyl glucosedioleate (E1A). ¹H NMR spectra were obtained as above for methyl glucosedioleate, polyglycerin-10 (Natrulon H-10 available from Lonza Group),and the polyglyceryl methyl glucose dioleate polyglyceryl thickener(E1A). Based on the reference spectra for methyl glucose dioleate andpolyglycerin-10, the proton peaks between 3-4 ppm in the spectra for thepolyglyceryl thickener were assigned to five protons of the polyglycerylrepeat units and five overlapping protons from the methyl glucosedioleate, and the proton peaks between 1-1.3 ppm were assigned to 40characteristic protons on the methyl glucose dioleate hydrophobic groups(See, for example, FIGS. 3 and 4). The areas under the curve for thepeaks were calculated and the DP_(g) calculated using the followingequation:

${DP}_{g} = \frac{\frac{\left\lbrack {{Area}_{3 - {4{ppm}}} - {5 \times \frac{{Area}_{1 - {1.3{ppm}}}}{40}}} \right\rbrack}{5}}{\frac{{Area}_{1 - {1.3{ppm}}}}{40}}$

Hydrophilicity Index Test:

The following Hydrophilicity Index Test was performed on variouspolyglyceryl thickeners using an Antaris FT-NIR Analyzer (Thermo FisherScientific, Waltham, Mass.) equipped with transmission, fiber-optic andintegrating sphere diffuse reflection modules. Real-time, on-line fiberoptic measurements were conducted using small diameter (⅛″) transmissionprobe (Axiom Analytical, Inc, Tustin, Calif.) immersed in the glasswarereactor. Off-line measurements were conducted using integrated spheremodule and the data analyzed using TQ Analyst software program providedby Thermo Fisher Scientific. The spectra from both, on-line and off-linemeasurements, were obtained using 64 scans with 4 cm⁻¹ resolution.

The Hydrophilicity Index (HI) test of the polyglyceryl thickener wasconducted on series of NIR spectra obtained from off-line, roomtemperature measurements using the integrated sphere module. HI is ameasure the relative proportions of hydrophilic (glyceryl units) vs.hydrophobic (hydrocarbon) character of the polyglyceryl thickenersproduced. Using TQ Analyst software, the area under the —OH absorptionband of glyceryl units (from 6,100 cm⁻¹ to 7500 cm⁻¹) was integrated andcompared with the area integrated under the hydrophobic, hydrocarbonspectral area (5320 cm⁻¹ to 6050 cm⁻¹). The calculated ratio betweenhydrophilic and hydrophobic area is HI, and can be used to compare thehydrophilicity between the different samples. HI ratio is independent ofthe sample size/thickness and test temperature. Lower values ofhydrophilicity index indicate less polyglycerol units have beenincorporated. Similarly, a higher hydrophilicity index will indicatethat more polyglycerol has been incorporated into the polyglycerylthickener. In certain preferred embodiments HI is about 0.3 or greater.More preferred is HI of about 0.4 or greater. In certain embodiments,preferred HI is from about 0.4 to about 0.9, and more preferred is HIfrom about 0.5 to about 0.8.

Zero Shear Viscosity Test:

The following Zero Shear Viscosity Test was performed on variouspersonal care compositions to determine the viscosity according to thepresent invention. Viscosities of test formulations were conducted at25° C. using a controlled-stress rheometer (AR-2000, TA InstrumentsLtd., New Castle, Del., USA). Steady-state shear stress sweeps wereperformed at 25.0±0.1° C. using a double-wall Couette geometry. Dataacquisition and analysis were performed with the Rheology Advantagesoftware v4.1.10 (TA Instruments Ltd., New Castle, Del., USA).Zero-shear apparent viscosities for samples that demonstrated Newtonianbehavior are reported as the average of viscosity values obtained over arange of shear stresses (0.005-100 Pa). For pseudoplastic(shear-thinning) fluids, zero-shear apparent viscosities (η₀) werecalculated via the fitting of shear stress sweep data to an Ellisviscosity model.

Formulation Foam Test:

The following Formulation Foam Test is performed on various cleansingcompositions to determine the foam volume upon agitation according tothe present invention. First, a solution of the test composition isprepared in simulated tap water. To represent the hardness of tap water,0.36 g of calcium chloride is dissolved in 995 g of DI water. Five (5.0)grams of test composition is then added to this solution and mixed untilhomogeneous. To determine the Formulation Foam Volume, the testcomposition (1000 mL) was added to the sample tank of a SITA R-2000 foamtester (commercially available from Future Digital Scientific, Co.;Bethpage, N.Y.). The test parameters were set to repeat three runs(series count=3) of 250 ml sample size (fill volume=250 ml) withthirteen stir cycles (stir count=13) for a 15 second stir time per cycle(stir time=15 seconds) with the rotor spinning at 1200 RPM(revolution=1200) at a temperature setting of 30° C.±2° C. Foam volumedata was collected at the end of each stir cycle and the average andstandard deviation of the three runs was determined The Maximum FoamVolume is reported as the value after the thirteenth stir cycle.

Example 1 Preparation of Polyglyceryl Thickeners (E1-E17)

Polyglyceryl thickener composition E1 was prepared as follows: to anappropriately-sized vessel fitted with N₂ sparge, reflux condenser,graduated addition funnel, and NIR reaction probe, 0.058 moles of methylglucose dioleate (MGD), 0.050 moles of glyceryl carbonate and 0.0058moles of Ca(OCH₃)₂ were added. The mixture was heated to about 80° C.and placed under vacuum to degas the mixture. The vacuum was broken andthe mixture then heated slowly to 190° C. under N₂ sparge withappropriate agitation. After equilibrating at 190° C. for 30 min, GC(degassed, 1.15 moles) was slowly added to the reactor over 2.5 hr.After completion of the addition, the reaction mixture was stirred at190° C. until all of the glycerol carbonate was consumed. All degassingsteps (moisture level measurements), reaction progress and GCconsumption were monitored in situ via real-time NIR analysis. After thereaction was complete the material was cooled and discharged to anappropriate container.

Additional polyglyceryl thickeners, E2-E17 were synthesized by varyingthe type or proportions of starting materials: polymerization initiator,glyceryl monomer, and/or base catalyst. The variation in startingmaterials used, reaction conditions, and products are summarized in theTable 1 below. For E9-E11, and E13 AGC, synthesized in accord with theprocedure below,and GC were added sequentially to the reaction mixture,whereas for E14, AGC and GC were added simultaneously. Additionally, thetime of addition, total reaction time and temperature of the variousreactions, as well as the resulting phases are shown in Table 2 below.The following abbreviations are used therein: MGD=methyl glucosedioleate, SO=sorbitan oleate, SSO=sorbitan sesquioleate, GC=glycerylcarbonate, AGC/GC=combination of acetylated glyceryl carbonate andglyceryl carbonate, SDO=sorbitan dioleate.

Preparation of acetyl glyceryl carbonate (AGC): the following is ageneral lab-scale procedure for the preparation of AGC: to a clean, dry250 mL two-neck flask equipped with a magnetic stirrer, near IR probe,and a condenser, was added glycerol carbonate (82.6 g, 0.70 mol), aceticanhydride (70.0 g, 0.68 mol), and two drops of pyridine. In the firststage of the reaction, the contents were heated under reflux for sixhours at 100° C. Conversion of glyceryl carbonate to AcGC was monitoredvia FT-NIR by following disappearance of the characteristic —OH(hydroxyl) absorption band for glyceryl carbonate at 7000 cm⁻¹. In thesecond stage of the reaction, the acetic acid byproduct was removed viadistillation at 45° C. under reduced pressure (ultimate vacuum=3.5Torr). Removal of acetic acid was monitored via near IR by following thedisappearance of the acetic acid peak at 6850 cm⁻¹. The resulting AcGCwas stored under nitrogen blanket until use.

TABLE 1 Synthesis of E1-E17 Polymerization Initiator Glyceryl monomerBase catalyst Ex. # type moles type moles type moles E1 MGD 0.0575 GC1.1499 Ca(OCH₃)₂ 0.0058 E2 MGD 0.0575 GC 1.2740 Ca(OCH₃)₂ 0.0058 E3 MGD0.0575 GC 1.1499 KOCH₃ 0.0116 E4 MGD 0.0575 GC 0.8413 K₂CO₃ 0.0058 E5MGD 0.0575 GC 1.1300 KGC (20%) 0.0028 E6 MGD 0.0575 GC 1.1525 K₂CO₃0.0057 E7 MGD 0.0575 GC 1.1499 KOC(CH₃)₃ 0.0058 E8 MGD 0.0575 GC 1.1240KGC (10%) 0.0029 E9 MGD 0.0349 AGC/GC 0.7150/ KOCH₃ 0.0035 (seq) 1.1431E10 MGD 0.0575 AGC/GC 0.0440/ KOCH₃ 0.0035 (seq) 1.149 E11 MGD 0.0575AGC/GC 0.1300/ KOCH₃ 0.0035 (seq) 0.5655 E12 MGD 0.0575 GC 0.5710Ca(OCH₃)₂ 0.0058 E13 MGD 0.0575 AGC/GC 0.187/ KOCH₃ 0.0035 (seq) 0.571E14 MGD 0.0575 AGC/GC 0.187/ KOCH₃ 0.0035 (random) 0.571 E15 SO 0.0575GC 1.1499 Ca(OCH₃)₂ 0.0057 E16 SSO 0.0575 GC 1.1499 Ca(OCH₃)₂ 0.0057 E17SDO 0.0575 GC 1.1499 Ca(OCH₃)₂ 0.0057

TABLE 2 Reaction Conditions and Phase Nature of E1-E17 ReactionConditions Total reaction time add. time Temperature Ex. # (hrs) (hrs)(° C.) Product E1 2.5 4.30 190 two- phase E2 2.5 5.53 190 two- phase E33.17 4.17 190-200 two- phase E4 6.00 6.00 190-200 two- phase E5 5.507.00 190 two- phase E6 9.50 10.00 190-200 two- phase E7 7.80 8.17 190two- phase E8 3.75 5.00 180 two- phase E9 1.75 10.95 175 one- phase E102.50 4.75 180 two- phase E11 3.46 6.30 180 two- phase E12 2.43 3.51 190two- phase E13 5.25 6.25 180 two- phase E14 3.83 4.83 180 one- phase E152.75 5.00 190 two- phase E16 2.66 4.66 190 two- phase E17 3.17 5.17 190two- phase

The results above indicate that in nearly all cases (except E9 and E14),the reaction product included two-phases. It was observed that the topphase was less viscous and lighter in color than the bottom phase.

Example 2 Properties of Polyglyceryl Thickeners

Examples E1-E17 were characterized for Average Degree of GlycerylPolymerization and Hydrophilicity Index in accord with the respectiveProcedure and Test above. For those reaction products that included twophases, the phases were separated from one another by decanting off thetop layer. The top phase/layer was identified as “A” and the bottomphase was identified as “B.” For example, the top phase of InventiveExample, E1 is identified as Inventive Example E1A, whereas the bottomphase of Inventive Example E1 is identified as Example E1B. AverageDegree of Glyceryl Polymerization and Hydrophilicity Index for theresulting compositions are reported in Table 3 below.

TABLE 3 Properties of Inventive Polyglyceryl Thickeners EX. # GlycerylDP Hydrophilicity Index E1A 6.3 0.60 E1B 29.9 1.47 E2A 7.0 0.66 E2B 28.61.52 E3A 7.6 0.65 E3B 12.1 1.82 E4A 3.6 0.43 E5A 6.1 0.51 E5B 79.7 2.22E8A 4.0 0.48 E9 61.0 1.59 E10A 3.9 0.52 E10B 87.0 2.38 E11A 4.8 0.62E12A 5.1 0.52 E12B 38.8 1.16 E13A 6.8 0.63 E13B 17.0 1.61 E14 9.9 0.71E15A 24.6 1.15 E15B 47.6 1.82 E16A 27.0 1.11 E16B 38.6 1.69 E17A 6.30.66 E17B 37.9 1.72

From the results above, it appears that the top phases tended to have alow DP_(g) while the bottom phases tended to have a high DP_(g). Asexpected, and apparent from the data, DP_(g) correlates well withhydrophilicity index.

Also notable is the effect of degree of hydrophobic substitution.Inventive Examples E1-E14 used methyl glucose dioleate, which nominallyhas an average degree of substitution of hydrophobic moieties of 2.0,and therefore the nominal average number of hydrophobic groups perprimary linking group in these particular polyglyceryl thickeners is2.0/4=0.5. Inventive Example E15 uses sorbitan oleate, which nominallyhas an average degree of substitution of hydrophobic moieties of 1.0,and therefore the nominal average number of hydrophobic groups perprimary linking group in this particular polyglyceryl thickener is1.0/4=0.25. Inventive Example E16 uses sorbitan sesquioleate, whichnominally has an average degree of substitution of hydrophobic moietiesof 1.5 and therefore the nominal average number of hydrophobic groupsper primary linking group in this particular polyglyceryl thickener is1.5/4=0.375). Inventive Examples E15(A,B) and E16(A,B), which had lesshydrophobic substitution, tended to produce relatively high DP_(g)polyglyceryls, whereas the other Inventive Examples were more readilycapable of producing a broader range of DP_(g).

Example 3 Preparation of Comparative Examples (C1-C8) and Examples (E1 8to E42)

Liquid cleanser formulations were prepared as follows: to a beakerfitted with a mechanical stirrer and hotplate, water, ammonium laurylsulfate, and ammonium laureth sulfate were added. This was mixed atlow-medium speed and heat was slowly applied to the batch to increasethe temperature to 75° C. When the batch reached 75° C., cocamide MEAand a particular commercially-available thickener/test material wasadded. Heating was stopped after the ingredients were completelydissolved and the batch was allowed to cool to approx. 25° C., whilemixing was continued at medium speed. When the batch reached 25° C.,sodium chloride and DMDM hydantoin were added and mix until completelydissolved. pH was adjusted to 6.4±0.2 using citric acid or sodiumhydroxide solution. Water was added in q.s. to 100%. The composition ofthe various comparative compositions (and weight percentages ofingredients) are shown in the Table 4 below.

TABLE 4 Comparative Personal Care Compositions Thickening or TestMaterial/ Ingredient/INCI Tradename/ Name C1 C2 C3 C4 C5 C6 C7 C8Control Control — — — — — — — — (Unthickened) (Unthickened) NatrulonH-10 Polyglycerin-10 — 5.00 — — — — — — Glucate DO Methyl Glucose — —5.00 — — — — — Dioleate Glucamate DOE-120 PEG-120 Methyl — — — 5.00 — —— — Glucose Dioleate Tego Care 450 Polyglyceryl-3 Methyl — — — — 5.00 —— — Glucose Distearate SPAN 80-NV-IQ-(AP Sorbitan Oleate — — — — — 5.00— — SPAN 83-NV-LQ- Sorbitan — — — — — — 5.00 — (AP) SesquioleateSorbitan Dioleate Sorbitan Dioleate — — — — — — — 5.00 Standapol A (28%)Ammonium Lauryl 10.92  10.92  10.92  10.92  10.92  10.92  10.92  10.92 Sulfate Standapol EA-2 Ammonium Laureth 4.39 4.39 4.39 4.39 4.39 4.394.39 4.39 (25%) Sulfate Comperlan 100 Cocamide MEA 1.24 1.24 1.24 1.241.24 1.24 1.24 1.24 (95%) Sodium Chloride Sodium Chloride 0.40 0.40 0.400.40 0.40 0.40 0.40 0.40 Glydant DMDM Hydantoin 0.06 0.06 0.06 0.06 0.060.06 0.06 0.06 Sodium Hydroxide Sodium Hydroxide q.s. q.s. q.s. q.s.q.s. q.s. q.s. q.s. solution (20%) Citric Acid solution Citric Acid q.s.q.s. q.s. q.s. q.s. q.s. q.s. q.s. (20%) Purified Water Water q.s. q.s.q.s. q.s. q.s. q.s. q.s. q.s. NATRULON H-10 is available from LonzaGroup of Allendale, NJ. GLUCATE DO and GLUCAMATE DOE-120 are availablefrom Lubrizol of Wickliffe, OH. TEGO CARE 450 is available from EvonikGoldschmidt GmbH of Essen, Germany. SPAN 80 and 83 are available fromCroda of Edison, NJ. STANDAPOL and COMPERLAN are available from CognisCorp. (now BASF) of Ambler, PA.

Inventive personal care compositions were also prepared in a similarmanner to the comparative personal care compositions of Table 4, exceptthat particular polyglyceryl thickeners of Example I were used. Thecompositions of the various formulations (and weight percentages ofingredients) are shown in the Table 5 (E18-E26), Table 6 (E27-E35), andTable 7 (Examples E36-E42), below.

TABLE 5 Personal Care Compositions with Polyglyceryl ThickenersThickening Material/ Tradename/ Ingredient/INCI Example Number Name E18E19 E20 E21 E22 E23 E24 E25 E26 E1A PGMGD 5.00 — — — — — — — — E1B PGMGD— 5.00 — — — — — — — E2A PGMGD — — 5.00 — — — — — — E2B PGMGD — — — 5.00— — — — — E3A PGMGD — — — — 5.00 — — — — E3B PGMGD — — — — — 5.00 — — —E4A PGMGD — — — — — — 5.00 — — E5A PGMGD — — — — — — — 5.00 — E5B PGMGD— — — — — — — — 5.00 Standapol A (28%) Ammonium Lauryl 10.92  10.92 10.92  10.92  10.92  10.92  10.92  10.92  10.92  Sulfate Standapol EA-2Ammonium Laureth 4.39 4.39 4.39 4.39 4.39 4.39 4.39 4.39 4.39 (25%)Sulfate Comperlan 100 Cocamide MEA 1.24 1.24 1.24 1.24 1.24 1.24 1.241.24 1.24 (95%) Sodium Chloride Sodium Chloride 0.40 0.40 0.40 0.40 0.400.40 0.40 0.40 0.40 Glydant DMDM Hydantoin 0.06 0.06 0.06 0.06 0.06 0.060.06 0.06 0.06 Sodium Hydroxide Sodium Hydroxide q.s. q.s. q.s. q.s.q.s. q.s. q.s. q.s. q.s. solution (20%) Citric Acid solution Citric Acidq.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. (20%) Purified Water Waterq.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s.

TABLE 6 Personal Care Compositions with Polyglyceryl ThickenersThickening Material/ Tradename/ Ingredient/INCI Example Number Name E27E28 E29 E30 E31 E32 E33 E34 E35 E8A PGMGD 5.00 — — — — — — — — E9 AGC/PGMGD — 5.00 — — — — — — — E10A AGC/PG MGD — — 5.00 — — — — — — E10BAGC/PG MGD — — — 5.00 — — — — — E11A AGC/PG MGD — — — — 5.00 — — — —E12A PGMGD — — — — — 5.00 — — — E12B PGMGD — — — — — — 5.00 — — E13AAGC/PG MGD — — — — — — — 5.00 — E13B AGC/PG MGD — — — — — — — — 5.00Standapol A (28%) Ammonium Lauryl 10.92  10.92  10.92  10.92  10.92 10.92  10.92  10.92  10.92  Sulfate Standapol EA-2 Ammonium Laureth 4.394.39 4.39 4.39 4.39 4.39 4.39 4.39 4.39 (25%) Sulfate Comperlan 100Cocamide MEA 1.24 1.24 1.24 1.24 1.24 1.24 1.24 1.24 1.24 (95%) SodiumChloride Sodium Chloride 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40Glydant DMDM Hydantoin 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06Sodium Hydroxide Sodium Hydroxide q.s. q.s. q.s. q.s. q.s. q.s. q.s.q.s. q.s. solution (20%) Citric Acid solution Citric Acid q.s. q.s. q.s.q.s. q.s. q.s. q.s. q.s. q.s. (20%) Purified Water Water q.s. q.s. q.s.q.s. q.s. q.s. q.s. q.s. q.s.

TABLE 7 Personal Care Compositions with Polyglyceryl ThickenersThickening Material/ Tradename/ Ingredient/INCI Example Number Name E36E37 E38 E39 E40 E41 E42 E14 AGC/PG MGD 5.00 — — — — — — (Rand) E15A PGSO— 5.00 — — — — — E15B PGSO — — 5.00 — — — — E16A PGSSO — — — 5.00 — — —E16B PGSSO — — — — 5.00 — — E17A PGSDO — — — — — 5.00 — E17B PGSDO — — —— — — 5.00 Standapol A (28%) Ammonium Lauryl 10.92  10.92  10.92  10.92 10.92  10.92  10.92  Sulfate Standapol EA-2 Ammonium Laureth 4.39 4.394.39 4.39 4.39 4.39 4.39 (25%) Sulfate Comperlan 100 Cocamide MEA 1.241.24 1.24 1.24 1.24 1.24 1.24 (95%) Sodium Chloride Sodium Chloride 0.400.40 0.40 0.40 0.40 0.40 0.40 Glydant DMDM Hydantoin 0.06 0.06 0.06 0.060.06 0.06 0.06 Sodium Hydroxide Sodium Hydroxide q.s. q.s. q.s. q.s.q.s. q.s. q.s. solution (20%) Citric Acid solution Citric Acid q.s. q.s.q.s. q.s. q.s. q.s. q.s. (20%) Purified Water Water q.s. q.s. q.s. q.s.q.s. q.s. q.s.

Example 4 Rheology of Compositions and Comparative Examples

The rheology of comparative Examples C1-C8 and Examples E18-E42 wasanalyzed according to the Zero Shear Viscosity Test to determine thethickening efficiency of the test material/thickener. The results ofthese tests are shown Table 8, below.

TABLE 8 Rheology and Appearance of Personal Care Compositions Example₀(cP) Rheology Type Appearance (qualitative) C1 941 Newtonian clear (nocolor) C2 79 Newtonian clear (no color) C3 — — opaque (nocolor)—unstable C4 575 Newtonian clear (no color) C5 20,450 Newtonianopaque (no color)—unstable over time C6 — Newtonian opaque (nocolor)—unstable C7 — Newtonian opaque (no color)—unstable C8 — Newtonianopaque (no color)—unstable E18 6600 Newtonian clear (light amber color)E19 43 Newtonian clear (amber color) E20 9671 Newtonian hazy (lightstraw color) E21 1193 Newtonian hazy (light amber color) E22 8067Newtonian hazy (light straw color) E23 3000 Newtonian hazy (light ambercolor) E24 2777 Newtonian opaque (light straw color) E25 2788 Newtonianhazy (light straw color) E26 43 Newtonian opaque (light straw color) E272948 Newtonian opaque (straw color) E28 16 Newtonian clear (amber color)E29 3841 Newtonian opaque (light straw color) E30 21 Newtonian clear(light straw color) E31 4678 Newtonian hazy (light straw color) E32 3517Newtonian opaque (straw color) E33 170 Newtonian hazy (straw color) E346657 Newtonian clear (light straw color) E35 66 Newtonian clear (lightstraw color) E36 905 Newtonian clear (light straw color) E37 326Newtonian slight haze (light straw color) E38 92 Newtonian clear (lightstraw color) w/small precipitate E39 476 Newtonian slight haze (lightstraw color) E40 159 Newtonian clear (light straw color) w/smallprecipitate E41 2274 Newtonian hazy (light straw color) E42 229Newtonian hazy (light straw color)

As can be seen in Table 8, the comparative examples showed no ability tothicken the base “control” formulation (Comparative Example C1). Theonly comparative example which showed some apparent initial ability tothicken was Comparative Example C5, which used Polyglyceryl-3 MethylGlucose Distearate (believed to be a polyglyceryl emulsifier with aDP_(g) of 3, a methyl glucose residue node structure). However,Comparative Example C5 was not stable and phase separated when standingat room temperature overnight. By comparison the tested Examples of thepresent invention have show stability while standing at room temperaturefor at least several months, to a year, or more.

Furthermore, to show the effect of DP_(g), FIG. 1 shows Zero ShearViscosity plotted vs. DP_(g) for Inventive Examples E18 to E42. It isclear from the Figure that those polyglyceryl thickeners with a DPgreater than 3 and less than about 11 built viscosity effectively,whereas those with a higher DP_(g) tend not to.

Also notable is the effect of average degree of substitution withhydrophobic moieties. Examples E37-E40, which as discussed above inExample 2, used a polyglyceryl compound with an average degree ofsubstitution of hydrophobic moieties of 1.0 or 1.5 (an average number ofhydrophobic groups per primary linking group of either 0.25 or 0.375respectively) did not build viscosity.

Example 5 Dose-Response Rheology of Compositions Comprising PolyglycerylThickeners

The following personal care compositions, Examples E43-56 were prepared.These compositions were tested for Zero Shear Viscosity to evaluate theeffect of polyglyceryl thickener concentration on viscosity. ExamplesE1A, E13A, E14, E15A, E16A, and E17A as well as Example E1B were testedin a formulation base that was identical to the base of Example 2. Theconcentrations and particular polyglyceryl thickeners are listed inTables 9a-c, below:

TABLE 9a Thickening Material/ Tradename/ Ingredient Example Number NameE18 E43 E44 E19 E45 E46 E34 E47 E48 E1A PGMGD 5.00 — — — — — — — — E1APGMGD — 3.00 — — — — — — — E1A PGMGD — — 1.00 — — — — — — E1B PGMGD — —— 5.00 — — — — — E1B PGMGD — — — — 3.00 — — — — E1B PGMGD — — — — — 1.00— — — E13A AGC/PG MGD — — — — — — 5.00 — — E13A AGC/PG MGD — — — — — — —3.00 — E13A AGC/PG MGD — — — — — — — — 1.00

TABLE 9b Thickening Material/ Tradename/ Ingredient Example Number NameE36 E49 E50 E37 E51 E52 E39 E53 E54 E14 AGC/PG MGD 5.00 — — — — — — — —(Rand) E14 AGC/PG MGD — 3.00 — — — — — — — (Rand) E14 AGC/PG MGD — —1.00 — — — — — — (Rand) E15A PGSO — — — 5.00 — — — — — E15A PGSO — — — —3.00 — — — — E15A PGSO — — — — — 1.00 — — — E16A PGSSO — — — — — — 5.00— — E16A PGSSO — — — — — — — 3.00 — E16A PGSSO — — — — — — — — 1.00

TABLE 9c Thickening Material/ Tradename/ Ingredient Example Number NameE41 E55 E56 E17A PGSDO 5.00 — — E17A PGSDO — 3.00 — E17A PGSDO — — 1.00

The results are shown in FIG. 2. As can be seen from the figure, whenthickener concentration is increased over the range from 1 to 5 wt %compositions comprising (MGD w/GC) Sample 1A showed an increase of487-5659 cP (over the viscosity of the base), compositions comprising(MGD w/GC and AGC) Sample 13A (DP_(g) of 6.8) showed an increase of57-5716 cP, and compositions comprising (SDO w/GC) Sample 17A (DP_(g) of6.3) showed an increase of 860-1333 cP. Compositions comprising thepolyglyceryl thickener of Example E14, which has a DP_(g) of 9.9(Examples E36, 49 and 50) shows some “upward sloping” behavior ofviscosity versus thickener concentration.

However, compositions comprising the polyglyceryl compound of ExampleE16A, which has a DP_(g) of 27.0 and an average of 1.5 oleatehydrophobes, compositions with the polyglyceryl compound of ExampleE15A, which has a DP_(g) of 24.6 and a single oleate hydrophobe, andcompositions with the polyglyceryl compound of Example E1B which has aDP_(g) of 29.9 and two oleate hydrophobes, showed reduced viscosityversus the control which continued to decrease as the concentration ofpolyglyceryl compound was increased.

1. A method of making a polyglyceryl composition comprising reacting oneor more glyceryl monomers with a polymerization initiator of theformula:(Nu)_(b)-ZL′-(Hphob)]_(h) where: Z is a node structure that is not apolynucleophile remnant derived from sorbitan; each Nu is a nucleophilicgroup; each Hphob is a hydrophobic moiety; each L′ is a primary linkinggroup; h is 1 to 12; b is 1 to 11; h+b is at least 4; and h/h+b isgreater than 0.35.
 2. The method of claim 1 wherein the polymerizationinitiator is a polyol ester selected from the group consisting ofglucoside diesters, diglyceryl diesters, triglyceryl diesters, andcombinations of two or more thereof.
 3. The method of claim 2 whereinsaid one or more glyceryl monomers are selected from the groupconsisting of: glycerol carbonate, glycidol, glycerol carbonate C₁-C₄monoester, glycidol C₁-C₄ monoesters, and combinations of two or morethereof.
 4. The method of claim 3 wherein said one or more glycerylmonomers are selected from the group consisting of: glycerol carbonate,acetylated glyceryl carbonate, and combinations of two or more thereof.5. The method of claim 4 wherein said one or more glyceryl monomerscomprise glycerol carbonate and acetylated glyceryl carbonate.
 6. Themethod of claim 5 wherein said glyceryl carbonate monomer and saidacetylated glyceryl carbonate monomer are added simultaneously.
 7. Themethod of claim 5 wherein said glyceryl carbonate monomer and saidacetylated glyceryl carbonate monomer are added sequentially.
 8. Themethod of claim 7 wherein said acetylated glyceryl carbonate monomer isadded first and then said glyceryl carbonate monomer is added.
 9. Themethod of claim 1 wherein said reacting step further comprises reactingsaid one or more glyceryl monomers and said polymerization initiatorwith one or more comonomers selected from the group consisting ofethylene carbonate, 1,2-propylene carbonate,1,3-propylene carbonate, andcombinations of two or more thereof.
 10. The method of claim 1 whereinsaid reacting step results in a reaction product having two phases. 11.The method of claim 9 wherein said reacting step results in a reactionproduct having one phase.
 12. A method of making a polyglycerylcomposition comprising reacting two or more glyceryl monomers comprisingglyceryl carbonate monomer and acetylated glyceryl carbonate monomerwith a polymerization initiator of the formula:(Nu)_(b)-ZL′-(Hphob)_(h) where: Z is a node structure; each Nu is anucleophilic group; each Hphob is a hydrophobic moiety; each L′ is aprimary linking group; h is 1 to 12; b is 1 to 11; h+b is at least 4;and h/h+b is greater than 0.35.
 13. The method of claim 12 wherein thepolymerization initiator is a polyol ester selected from the groupconsisting of glucoside diesters, sorbitan diesters, diglyceryldiesters, triglyceryl diesters, and combinations of two or more thereof.14. The method of claim 12 wherein said glyceryl carbonate monomer andsaid acetylated glyceryl carbonate monomer are added simultaneously. 15.The method of claim 12 wherein said glyceryl carbonate monomer and saidacetylated glyceryl carbonate monomer are added sequentially.
 16. Themethod of claim 15 wherein said acetylated glyceryl carbonate monomer isadded first and then said glyceryl carbonate monomer is added.
 17. Themethod of claim 12 wherein said reacting step further comprises reactingsaid two or more glyceryl monomers and said polymerization initiatorwith one or more comonomers selected from the group consisting ofethylene carbonate, 1,2-propylene carbonate,1,3-propylene carbonate, andcombinations of two or more thereof.